c2 PDF

Chapter 2
N-Heterocyclic Carbene Complexes

in Additions to Multiple Bonds
Andreas A. Danopoulos
Abstract The use of N-heterocyclic carbene (NHC) complexes as homogeneous

catalysts in addition reactions across carbon-carbon double and triple bonds and
carbon-heteroatom double bonds is described. The discussion is focused on the
description of the catalytic systems, their current mechanistic understanding and
occasionally the relevant organometallic chemistry. The reaction types covered
include hydrogenation, transfer hydrogenation, hydrosilylation, hydroboration and
diboration, hydroamination, hydrothiolation, hydration, hydroarylation, allylic
substitution, addition, chloroesterification and chloroacylation.
2.1Introduction
The first isolation of stable cyclic and acyclic nucleophilic carbenes by Arduengo
and Bertrand, and the development of synthetic methods for their introduction to
metals, either by direct reactions with metal precursors of the preformed, or in situ
generated carbenes, or by the silver transmetallation methodology, initiated detailed
studies aiming at a better understanding and use of these ligands in homogeneous
catalysis. The current refined description of the metal-NHC bonding across the
Periodic Table and the factors affecting it, the semi-quantitative parametrisation of
the ligand topology and the space it occupies around the metal, the dynamic processes in which N-heterocyclic carbene (NHC) ligands are involved, and the invention of ways to introduce ligand chirality, provide the essential tools for further
catalyst discovery, tuning and development. In this chapter an overview of the use
of NHC complexes as catalysts in addition reactions across CC and C-heteroatom
multiple bonds is presented. The emerging picture is that NHC ligands are unique
in some catalytic applications and complementary to the well-established tertiary
phosphines, which we initially thought they were mimicking.
A. A. Danopoulos (*)
School of Chemistry, University of Southampton, Highfield SO17 1BJ, UK
e-mail: ad1@soton.ac.uk
C. S. J. Cazin (ed.), N-Heterocyclic Carbenes in Transition Metal Catalysis
and Organocatalysis, Catalysis by Metal Complexes 32,
DOI 10.1007/978-90-481-2866-2_2, Springer Science+Business Media B.V. 2011
23
24
A. A. Danopoulos
2.2Hydrogenation of Alkenes and Alkynes

The RhNHC complexes, with or without phosphine co-ligands, have been studied as
hydrogenation catalysts of alkenes with molecular hydrogen, with the aim to develop
more active, selective (and/or enantioselective) and thermally stable catalysts.
Rh(III)(NHC) hydrides have been studied as catalysts for this type of hydrogenation. The products from the reaction of Rh(I) complexes with H2 are dependent
on the nature of the NHC. The reaction of [RhCl(IPr)2(N2)] 1 (IPr = N,N-bis-[2,6(di-iso-propyl)phenyl]imidazol-2-ylidene) with H2 gave the monomeric complex 3
[1], which was also obtained from the reaction of [RhCl(COE)(IPr)]2 2 with H2 and
excess IPr, while the reaction of [RhCl(COE)(IMes)]2 with H2 gave the chloride
bridged species 4 (Scheme2.1) [2].
IPr
Cl Rh N2
IPr
1
COE
Rh
or
IPr
Cl
Cl
Rh
IPr
H2
COE
IPr
H
H
Cl Rh
IPr
3
COE
IMes
Cl
Rh
Rh
COE
Cl
IMes
H2
H
H
IMes
Cl
Rh
Rh
H
Cl
IMes
H
4
Scheme2.1 Reactions of Rh(I) NHC complexes with hydrogen
[Rh(COE)2Cl]2 in the presence of IMes, N,N-bis-[2,4,6-(trimethyl)phenyl]imidazol-2-ylidene, reacted with H2 at room temperature to give the trigonal bipyramidal [Rh(H)2Cl(IMes)2] 6 (which is analogous to 3) via intermediate formation of the
isolable cyclometallated 5 (Scheme2.2) [3].
N
COE
Rh
COE
Cl
Cl
Rh
COE
COE
IMes
THF, RT
N
Rh
Cl
N
H
N
N
H2
N
Rh
Cl
N
H
H
N
Scheme2.2 The formation of the rhodium dihydride complex via a cyclometallated intermediate
The hydrogenation activity of the isolated hydrides 3 and 6 towards cyclooctene

or 1-octene was much lower than the Wilkinsons complex, [RhCl(PPh3)3], under the
same conditions [2]; furthermore, isomerisation of the terminal to internal alkenes
competed with the hydrogenation reaction. The reduced activity may be related to
the high stability of the Rh(III) hydrides, while displacement of a coordinated NHC
by alkene may lead to decomposition and Rh metal formation.
The catalytic hydrogenation of alkenes by mixed NHC/phosphine complexes of
rhodium was also studied. Initial results of the hydrogenation of cyclohexene by
trans-[RhCl(ICy)(L)2] (ICy = N,N-(dicyclohexyl)imidazol-2-ylidene, L = PPh3,
25
2 N-Heterocyclic Carbene Complexes in Additions to Multiple Bonds
P(OPh)3) and trans-[RhCl(ICy)2PPh3] showed poor activity compared to Crabtrees

catalyst [Ir(1,5-COD)(Py)(PCy3)][PF6] or its IMes analogue, [Ir(1,5-COD)(Py)
(IMes)][PF6], under the same conditions [4, 5]. Systematic optimisation was conducted by generating the catalysts in situ from [RhCl(1,5-COD)(ICy)] and two or
four equivalents of PPh3 under H2 [5]. In these studies an induction period was
observed, while the phosphine was required to prevent catalyst decomposition.
The activities were one fifth to one tenth of the original Wilkinsons catalyst. The
reduced activities may be ascribed to reduced phosphine pre-dissociation to form the
coordinatively and electronically unsaturated active species. In view of the observation that NHCs dissociate from [RhCl(NHC)(L)2] in the presence of L, it may be that
the active species of the in situ systems contains only phosphine ligands [6].
Chiral monodentate carbene complexes of Rh and Ir of the type [MCl(1,5-COD)
(NHC)] (M = Rh, Ir) with the ligands 79 (Fig.2.1) have been studied as catalysts
for the enantioselective hydrogenation of methyl-2-acetamido acrylate. Even
though the activities were high, the enantiomeric excesses (ee) were poor [7, 8].
N
7
N R
R N
R
R
9 R = -methyl-benzyl
8a R = Ph
8b R = -methyl-benzyl
Fig.2.1 Chiral NHC ligand designs used in the Rh-catalysed enantioselective hydrogenation of
methyl-2-acetamido acrylate by dihydrogen
Replacement of one PCy3 in [RuCl(H)(CO)(PCy3)2] 10 by IMes gave [RuCl(H)

(CO)(PCy3)(IMes)], 11 (Fig.2.2) which is an active catalyst for the direct hydrogenation
of 1-hexene, allylbenzene and cyclooctene. At higher temperatures (ca. 100C) the
activity of 11 is superior to 10. Furthermore, small (12 equiv.) quantities of HBF4Et2O
act as co-catalyst, by enhancing the dissociation of PCy3 (through the formation
of [PCy3H+][BF4]) [9]. Similar behaviour was observed in the hydrogenation of
1-octene by [Ru(CO)(Cl)(Ph)(PCy3)(SIMes)], 12 [10]. [RuCl(H)(CO)(PPh3)(NHC)]
(NHC = IMes, SIMes), 13, is more active for the hydrogenation of cyclooctene or
cis- and trans-cyclododecene [11] due to the increased lability of PPh3 compared to
PCy3. In the latter case isomerisation competes with hydrogenation [12].
PCy3
Cl
Ru H
OC
PCy3
10
NHC
Cl
Ru R
OC
IMes
L
11 R = H, L = PCy3, NHC = IMes
12 R = Ph, L = PCy3, NHC = SIMes
13 R = H, L = PPh3, NHC = IMes
14 R = H, L = PPh3, NHC = SIMes
Fig.2.2 Ruthenium-based hydrogenation catalysts bearing NHC ligands
SIMes
26
A. A. Danopoulos
Reaction of the 18e-species [Ru(H)2(CO)(IMes)(PPh3)2] 15 with trimethyl vinylsilane gave the cyclometallated complex 16 and trimethylethylsilane; 16 can be converted
to the original dihydride 15 by reaction with H2 (1 atm, room temperature) or iPrOH
(50C) [13]. Catalytically, vinylsilane can be hydrogenated by 16 in iPrOH in quantitative
yield (Fig.2.3) [14].
N
Ph3P
OC
N
H
Ru H
PPh3
15
N
H
OC Ru C
H2
Ph3P
PPh3
16
Fig.2.3 Ru-IMes and cyclometallated Ru-IMes complexes used as catalysts for the hydrogenation
of trimethylvinylsilane
Reduction of acetophenone by iPrOH/H2 has been studied with the ruthenium

complexes [Ru(H)(h2-BH4)(CO)L(NHC)], (L = NHC, PPh3, NHC = IMes, IPr,
SIPr). The activity of the system is dependent on the nature of the NHC and
requires the presence of both iPrOH and H2, implying that transfer and direct
hydrogenation mechanisms may be operating in parallel [15].
Replacement of the pyridine in Crabtrees complex by NHC (NHC = IMes, IMe)
gave very active catalysts for the hydrogenation by H2 of various alkenes to alkanes,
including hindered tertiary and quaternary alkenes. For terminal 1-alkenes (1-octene),
the IMes analogue gives best conversions, while for tertiary and quaternary alkenes
(1-methyl-cyclohexene and 2,3-dimethyl-2-butene) the IMe analogue is more suitable
[16]. On the other hand, replacement of PCy3 by NHC (NHC = IMes, ICy, SIMes) in
Crabtrees complex [Ir(1,5-COD)(Py)(PCy3)]+, gave a catalyst for the hydrogen transfer reduction of aryl- and alkyl-ketones to alcohols, cyclic alkenes to alkanes, dienes
to alkenes, a,b-unsaturated carbonyl compounds to alcohols, and aromatic nitro compounds to anilines. Best activities were observed with NHC = ICy [12].
Initial attempts to develop PdNHC complexes as hydrogenation catalysts for
alkenes or alkynes focused on the use of [Pd(NHC)2] species. However, these did
not withstand the reaction conditions decomposing to metallic Pd and imidazolium
salts or imidazolidine, presumably after H2 oxidative addition to form Pd(NHC)
hydrides, followed by imidazolium elimination. Reports by Elsevier on the stability
of Pd(NHC) fragment under hydrogenation conditions opened the way for the
development of Pd(NHC) hydrogenation catalysts [17]. The catalysts proved very
selective for the semi-hydrogenation of arylalkynes to Z-alkenes with high
chemo- and stereo-selectivity, being far superior than the known Pd(bipy) and
Pd(diazabutadiene) based complexes. The catalysts were best generated in situ
from a Pd(0) source, preferentially 17, an imidazolium or imidazolidinium salt and
KOtBu, at room temperature, in the presence of the alkyne and H2 (1 atm).
Surprisingly, better activities were observed with the unsaturated imidazol-2ylidene precursors such as 18. Preformed Pd(NHC) complexes, for example 19,
were not as active as the in situ generated catalysts (Fig.2.4).
Mes N
N + N
Cl
Pd
O
O
17
27
N Mes
R
Pd
R
R
19
R = COOMe
18
Fig.2.4 Components of the Pd-based catalytic system for the hydrogenation of arylalkynes. The
pre-formed complex 19 shows reduced activity
Recently, the direct hydrogenation of a wide range of alkenes was successfully

carried out using [Pd(SIPr)(PCy3)] 20 in alcohols or THF. Complex 20 in the presence of H2 forms trans-[Pd(H)2(SIPr)(PCy3)]. The activity of the catalytic system is
very high under mild conditions (1 bar, rt, 0.25 mol%Pd). Reduction of the alkene
functionality can be selective in a,b-unsaturated carbonyl compounds, while alkynes
can be semi-hydrogenated to Z-alkenes with good selectivity as seen above [18].
Bidentate NHC-Pd complexes have been tested as hydrogenation catalysts of
cyclooctene under mild conditions (room temperature, 1 atm, ethanol). The complex 22 (Fig.2.5), featuring abnormal carbene binding from the C4 carbon of the
imidazole heterocycles, has stronger PdCNHC bonds and more nucleophilic metal
centre than the C2 bound normal carbene chelate 21. The different ligand properties are reflected in the superior activity of 22 in the hydrogenation of cyclooctene
at 12 mol% loadings under mild conditions. The exact reasons for the reactivity
difference in terms of elementary reaction steps are not clearly understood [19].
N
N
N
i Pr
2BF4
NCMe
Pd 2 +
NCMe
N
iPr
21
i Pr
N
N
N
2BF4
NCMe
Pd 2 +
NCMe
N
22
i
Pr
Fig. 2.5 Palladium-based hydrogenation catalysts with bidentate normal and abnormal
NHC ligands
The development of functionalised NHC ligands, bearing NHC functional

group(s) tethered to classical donors, provides additional ways of tuning the coordination sphere of the metal both sterically and electronically, and opens new ways for
catalyst design. The chiral complexes 23, 24 and 25 (Fig.2.6) have been used for the
enantioselective hydrogenation of substituted aryl alkenes (23 and 24), functionalised
alkenes 24 and a,b-unsaturated esters 25 with good ees. The oxazoline carbene species (23 and 24) operate under milder conditions than analogous complexes where
NHC is replaced by phosphine [2023]. Theoretical calculations on the mechanism
of hydrogenation of the arylalkenes with 23 and the origin optical induction, support
an Ir(III)/(V) cycle with rate determining metathetical insertion of the hydride to a
28
A. A. Danopoulos
coordinated alkene. The face selectivity is determined by the interaction of the

1-adamantyl substituent of the oxazoline with the phenyl group of the substrate [24].
N
N
R
N
Ir +
N
R
R'
23
R = 2,6-iPr-C6H3
R' = 1-adamantyl
Ir +
Ph
N
Ph
R'
i
[BArf4]
Pr
24
R = tBu
R' = neopentyl, t Bu, i Bu
PPh2
Rh+
[BF4]
25
Fig.2.6 Chiral functionalised NHC complexes as enantioselective hydrogenation catalysts with

dihydrogen
The supported Au complexes presented in Scheme2.3 show increased activity in the

hydrogenation by H2 of diethylcitraconate 26 and diethylbenzylidene succinate 27,
compared to [AuCl(PPh3)] (40C, 4 atm, ethanol). The nature of the support has an
effect on the TOF (turnover frequency) of the reaction, being highest with ITQ-2 and
lowest with silica. The preferred mechanism of hydrogen activation involves heterolytic
splitting rather than homolysis or oxidative addition steps [25].
COOEt
H
EtOOC
COOEt
27
26
Mes
N
AuCl
Si(OEt)3
HO
HO
O
support
HO
Mes
Si O
AuCl
O
H
support = silica, MCM-41, ITQ2
support
EtOO
Scheme2.3 Hydrogenations catalysed by a supported Au-NHC complex
2.3Transfer Hydrogenation and Related Reactions

The transfer hydrogenations of carbonyl compounds to alcohols catalysed by a
variety of NHC complexes have been intensively studied. The strong MCNHC bond
and the excellent s-donating properties of the NHC ligands are responsible for the
stabilisation of hydrides and alkoxides that are intermediates in the postulated catalytic
cycles. Rh, Ir, and Ru species, where the metal is coordinated by monodentate NHCs
and classical co-ligands (pyridine, phosphines or cyclopentadienyl analogues) [2628],
29
pincer pyridine di-carbenes [29, 30] bidentate di-carbenes [31] and functionalised
NHCs [28, 3235] are particularly successful catalysts. Steric and electronic tuning
of the coordinated NHCs is important for the successful catalysts. Less hindered,
alkyl substituted NHCs usually give more active catalysts than their analogues with
bulky aryl substituents. The influence of the electronic properties of the NHC on
activity and selectivity is more subtle. For example, imidazol-based NHC complexes
are generally most active for the reduction of ketones, while in specific cases rhodium
complexes with abnormal C4 bound NHCs are more active compared to C2 bound
analogues [36]; iridium complexes with the weaker s-donating triazol based NHCs
have been developed for the reduction of imines, alkenes and the stepwise one-pot
reductive amination of aldehydes [27]. However, the structure and property principles
underlying catalyst tuning are still underdeveloped with these ligand systems and the
NHC ligands in general. Co-ligands (for example pyridine donors, cyclopentadienyl
analogues, etc.) are also important in the catalyst design, presumably by stabilising
the metal in the active oxidation state, or providing labile sites for substrate coordination. In addition, in polydentate functionalised NHC complexes, a possible hemilability of the tethered classical donor has been implied during catalysis and supported by
spectroscopic studies [34, 37].
In the majority of the known examples, the donor of hydrogen equivalents is
isopropanol; HCOO or HCOOH/Et3N azeotrope are less successful. Aromatic
ketones (mainly acetophenone and benzophenone) were the easiest to reduce even
under mild conditions and low catalyst loadings.
The required bases for the reaction include KOH, KOtBu and K2CO3, the latter usually added in higher base/substrate ratios than KOH. However, K2CO3 is the base of
choice for the reduction of aldehydes, where aldehyde decarbonylation and subsequent
catalyst deactivation or formation of aldol side products interfere with the reduction [38].
The transfer hydrogenation of imines is more challenging due to competing formation
of the catalytically inactive complex involving s-coordination of the imine, and therefore
NHC based catalysts for this purpose are less common [27, 29, 39]. The activity of
certain NHC complexes in imine reduction has been exploited for the one-pot sequential
reductive amination of aldehydes to amines. In the reported system, the added base
K2CO3 acts also as a drying agent during the imine formation [27]. Selected complexes
that have been studied as transfer hydrogenation catalysts and related catalytic data are
shown in Figs.2.7 and 2.8 and Tables2.1 and 2.2, respectively.
Two versatile hydrogen auto-transfer processes were catalysed by the iridium complexes 41 and 42 [28, 40]. The first, N-alkylation of primary amines using alcohols as
electrophiles, involves oxidative hydrogen elimination from the alcohol to form an
aldehyde, which, in the presence of amine, is converted to imine and the latter reduced
to the secondary amine by transfer hydrogenation. The second system involves oxidative hydrogen elimination from one primary and one secondary alcohol to form an
aldehyde and ketone, respectively, which undergo aldol coupling and reduction of the
a,b-enone to alkylated alcohols. Both transformations are very attractive compared to
conventional alkylations with organic halides, due to their reduced waste [41]. The
reactions are carried out in refluxing toluene in the presence of base (KOH, KOtBu,
NaHCO3) with high conversions at low catalyst loadings (1.0 mol%).
30
A. A. Danopoulos
R
+
Ir
PF6
+
Ir
N
py
R
29
N N PF6
N
R
L
30
Ir
31 Br
OMe
R = Mes, Cy
Fig.2.7 Selected NHC complexes that have been studied as transfer hydrogenation catalysts
Mes
N
R
N
I
Ir
N
N
N
O
37
R = 2,6-iPr-C6H3
N
M+
Ir
35
Cl
N
R
N
N
I
I
Rh I Rh
N
R
Ru
N
N
36
PF6-
PF6
M
N
N
Cl
Br
Br
R
R
L
38 M = Ru, L = CO
39 M = Rh, L = Cl
R
33 M = Rh
34 M = Ir
N
Ru
N
N
Cl
R Ph3P Cl
R
Cl
N Cl
R
32
Cl
Ph
+
Ir
N
N
N
Ir
N
R
N
41
N
40
42
Fig.2.8 Selected NHC complexes that have been studied as transfer hydrogenation catalysts
Table2.1 Selected transfer hydrogenation data of R1R2C=O, R1= alkyl, phenyl, R2 = alkyl, H or
Ph. All reactions were carried out in refluxing iPrOH (82C)
Complex
(mol%)
Base (subst./base)
Time (h)
Conv. (%)
R1
R2
Ref
Ph, Ar
Me
32 (0.01)
KOH (2000/1)
2
98
[31]
p-tolyl
H
32 (0.1)
K2CO3 (2:1)
0.25
98
[38]
Ph
Me
40/41 (1.0)
KOH (10:1)
3
98
[28]
Ph
Me
37 (0.015)
KOtBu (10:1)
12
80
[29]
Ph
Me
39 (0.006)
KOH (2:1)
6
30
[30]
Ph
Me
31 (0.5)
KOH (20:1)
1.5
98
[35]
Me
32 (0.1)
KOH (200:1)
24
88
[42]
Bun
(CH2)5
(CH2)5
(CH2)5
(CH2)5
Ph
Ph
Ph
Ph
Ph
Ph
38 (0.005)
41 (0.1)
40 (1.0)
31 (0.5)
36 (0.5)
39 (0.006)
34 (0.1)
KOH (2:1)
KOH (1:1)
KOH (10:1)
KOH (20:1)
KOH (10:1)
KOH (2:1)
KOH (2:1)
20
4.5
5
2
2
24
2
65
99
99
98
97
98
99
[30]
[28]
[28]
[28]
[36]
[30]
[32]
31

Table2.2 Transfer hydrogenation of N-benzylidene aniline. Solvent is iPrOH
Complex (mol%) Base (base:substr.) T (C) Time (h) Conv. (%)
37 (0.015)
55
20
6070
KOtBu (10:1)
30 (1.0)
K2CO3 (2:1)
82
0.5
92100
40 (1.0)
KOH (10:1)
82
5
7080
Ref
[29]
[27]
[28]
Transfer hydrogenation of aldehydes with isopropanol without addition of external base has been achieved using the electronically and coordinatively unsaturated
Os complex 43 as catalyst. High turnover frequencies have been observed with
aldehyde substrates, however the catalyst was very poor for the hydrogenation of
ketones. The stoichiometric conversion of 43 to the spectroscopically identifiable
in solution ketone complex 45, via the non-isolable complex 44 (Scheme 2.4),
provides evidence for two steps of the operating mechanism (alkoxide exchange,
b-hydride elimination to form ketone hydride complex) of the transfer hydrogenation reaction [43].
i
PrOH
Os+ OTf H O
2
OH
IPr
Os+ OTf
O
IPr
43
Os+
IPr
44
H
45
OTf
Pr
iPr
i
N Pr
IPr Pri
Scheme2.4 Experimental evidence in support of the mechanism for the base-free transfer
hydrogenation of carbonyl compounds catalysed by complex 43
The iridium complex 35 has been also used as catalyst for the transfer hydrogenation of substituted nitroarenes [34]. Good to very good conversions were
observed (2.5 mol%, in refluxing isopropanol, 12 h). A mixture of two products was
obtained, the relative ratio of which depends on the concentration of added base
(KOH) and catalyst. (Scheme2.5)
Mes
NH2
NO2
[Ir]
KOH, iPrOH
Br
N
+ Br
Br
46
N
47
Br
N
N
Ir
35
Cl
Scheme2.5 Products formed in the transfer hydrogenation reduction of nitroarenes by complex 35
This behaviour was rationalised by a stepwise reduction mechanism, in which a

high catalyst or KOH concentration gives a high hydride concentration and leads to
the aniline formation and suppression of intermolecular reactions to the dimeric
azo-compound.
32
A. A. Danopoulos
2.4Hydrosilylation Reactions
The hydrosi(ly)lations of alkenes and alkynes are very important catalytic processes
for the synthesis of alkyl- and alkenyl-silanes, respectively, which can be further transformed into aldehydes, ketones or alcohols by established stoichiometric organic
transformations, or used as nucleophiles in cross-coupling reactions. Hydrosilylation
is also used for the derivatisation of Si containing polymers. The drawbacks of the
most widespread hydrosilylation catalysts [the Speiers system, H2PtCl6/iPrOH, and
Karstedts complex [Pt2(divinyl-disiloxane)3] include the formation of side-products,
in addition to the desired anti-Markovnikov SiH addition product. In the hydrosilylation of alkynes, formation of di-silanes (by competing further reaction of the product
alkenyl-silane) and of geometrical isomers (a-isomer from the Markovnikov addition
and Z-b and E-b from the anti-Markovnikov addition, Scheme2.6) are also possible.
R
R'3Si-H
Pt-catalyst
R'3Si
-isomer
R'3Si
R'3Si
R
-E-isomer
-Z-isomer
Scheme2.6 Possible isomeric products in the hydrosilylation of alkynes (disilanes from further
hydrosilylation of the alkenyl silanes are excluded)
Therefore, improved chemo- and stereo-selectivities of the catalysts are

c hallenging goals of current research in the area. The reduced chemoselectivity and
the formation of side-products with the Speier and Karstedt catalysts is attributed
to poor catalyst stability under the reaction conditions, and efforts to improve it
have focused on the use of NHC ligand designs, taking advantage of the high
strength of the PtCNHC bond.
R
NHC Pt
Si
Si
48 NHC = ItBu
49 NHC = ICy
50 NHC = IMes
51 NHC = SIMes
52 NHC = IPr
53 NHC = SIPr
ICy Pt
R3Si
N
ICy Pt
H
54
N
ICy
R3SiH
ICy Pt
56
55
N
ItBu
N
SiR3
Pt ICy
N
IMes
SIMes
iPr
iPr
iPr
iPr
Si
R3
N
Pr
IPr iPr
N
iPr
SIPr iPr
Scheme2.7 Platinum-NHC complexes as hydrosilylation catalysts
Complexes of the type 4853 (Scheme2.7) have been targeted as pre-catalysts

for the hydrosilylation of alkenes [44]. For example, in the hydrosilylation of
1-octene with (Me3SiO)2Si(Me)H, which was studied in detail as a model reaction,
the activity of complexes 4849 with alkyl substituted NHC ligands, is inferior to
that of the Karstedts system. However, selectivity and conversions are dramatically improved due to the suppression of side-product formation. In this reaction
33
only the anti-Markovnikov addition product is observed. The complexes 5052

with bulky aryl substituted NHCs, show activity comparable to that of the Karstedts
complex with excellent chemo- and regio-selectivity, even though they exhibit variable induction periods. The higher activity is attributed to electronic factors and the
steric organisation around the Pt imposed by the ligand; the induction period is
possibly due to slow diene dissociation from the pre-catalysts to form the underligated Pt-NHC active species. Further insight into the nature of the catalytic species was obtained by the reaction of 49 with excess silane, leading to the isolation
of 54, which was fully characterised; 54 converts to the active monomeric catalyst
55 by cleavage of the weakly bound dimer and loss of silane. Based on kinetic data,
the reaction of 54 with alkene and silane is more likely to proceed via the concerted
transition state 56 rather than two distinct oxidative addition and insertion elementary
steps. Hydrosilylation of styrene with Et3SiH catalysed by 51 (formed in situ from
Pt(norbornene)3 and SIMesHCl/KOtBu) also gave excellent conversions (~99%)
with high selectivity (ca. 82%) to the anti-Markovnikov product [45].
The hydrosilylation of alkynes has also been studied using as catalysts Pt, Rh, Ir
and Ni complexes. The improvement of the regioselectivity of the catalyst and the
understanding of stereoelectronic factors that control it have been major incentives
for the ongoing research. From numerous studies involving non-NHC catalysts, it
has been established that there is a complex dependence of the product ratio on the
type of metal, the alkyne, the metal coordination sphere, the charge (cationic versus
neutral) of the catalytic complex and the reaction conditions. In the Speiers and
Karstedts systems, mixtures of the thermodynamically more stable a- and b-Eisomers are observed. Bulky phosphine ligands have been used on many occasions
in order to obtain selectively b-E-isomers.
The Pt complexes 4853 mentioned previously are pre-catalysts for the hydrosilylation of 1-octyne with bis-(trimethylsilyloxy)methylsilane and other silanes [46].
Complexes 52 and 53 provide good conversions at very low loading (0.005 mol%)
with high selectivity (10:1) for the b-E-isomer. Further studies have pointed to the
steric influence of the o-groups of the aryl substituents of the NHC as being responsible
for the high stereoselectivity. The linear correlation of the AH angle (see Chapter 1,
Fig.1.16) of the NHC with the observed b-E-/a- ratio (larger AH angles in more
selective catalysts) was explained by the steric interactions between the out-of-thecoordination-plane aryl substituents of the NHC with the alkyne substituents prior
to the insertion step. In addition to steric interactions, electronic factors are also
responsible for the improved stereoselectivity.
The Rh and Ir complexes 5762 (Fig. 2.9) with functionalised N-heterocyclic
carbene ligands are also catalyst precursors for the hydrosilylation of alkynes. For
example, terminal alkynes were hydrosilylated with HSi(Me)2Ph in the presence of
57 or 58, yielding very good conversions to mixtures of the three possible stereoisomers, with preference for the b-E-isomer. A more detailed study of the catalytic
reaction profile using 58 showed that the b-Z-isomer was formed during the initial
stages of the reaction, and later isomerised to the thermodynamically more stable
E-isomer. Interestingly, hydrosilylations with HSi(OEt)3 showed preference for the
b-Z-isomer, without any tendency for isomerisation. Rationalisation of these data is
further complicated by the ambiguous nuclearity of the active catalysts originating
34
A. A. Danopoulos
from 58 and the exact coordination sphere of the active species [47]. On the other
hand, reactions catalysed by the cationic 57 gave from the outset the b-E-isomer.
N Me
N
N
N
+
Rh
Me
57
PF6
Rh
Br
R N
Rh
N
Br
N R
58 R = Me, nBu
N ( )n
Rh+ N BF
4
N
R
61 n = 2,3; R = Me, Mes
N
M+
PF6
N
n
Bu
59 M = Rh
60 M = Ir
NMe2
Cl ( )n
Rh
N
N
R
62 n = 2,3; R = Me, Mes
Fig.2.9 Hydrosilylation catalysts based on Rh- and Ir-NHC complexes
Complexes 59 and 60 catalyse the hydrosilylation of phenylacetylene (but not

other terminal alkyl alkynes) with HSi(Me)2Ph. Generally, the Rh analogue is more
active than the relative Ir. Both catalysts gave mixtures of all regioisomers, with a
preference for the b-Z-isomer, in contrast to what has been reported with other nonNHC cationic complexes of Rh, where the b-E isomers are predominating. Here
also the exact nature of the catalytic species is unclear [48].
Complexes 61 and 62 have been used for the hydrosilylation of a range of terminal alkynes with HSi(Me)2Ph. The product distribution is strongly dependent on
the nature of the alkyne and the catalyst. In general, catalysts with less bulky NHC
ligands are more active. With terminal alkynes substituted with small linear alkyls
(e.g. 1-hexyne), high conversions under mild conditions were obtained, and in some
cases very good selectivities for the b-Z-vinylsilane. In contrast, the hydrosilylations of Et3SiCCH gave predominantly the b-E-vinylsilane. These data have been
rationalised by postulating the classical Chalk-Harrod hydrosilylation mechanism
(SiH oxidative addition followed by alkyne insertion into the MSi bond to give
intermediate 63 and reductive elimination to the product b-E-vinylsilane).
Isomerisation of 6364 followed by reductive elimination leads to the b-Z-isomer.
With small alkyls on the alkyne-C (for example in 1-hexyne), intermediate 64 is
favoured due to reduced RhSiR3 interaction leading to product b-Z. Larger alkyls
on the alkyne-C result in reduced selectivities due to the establishment of an equilibrium between 63 and 64. On the other hand, in the hydrosilylation of Et3SiCCH,
electronic factors are more important in determining the stability of 63 relative to
64 leading to substantial amounts of b-E-vinylsilane (Scheme2.8) [49].
35
Si
H
[Rh]
R
H
[Rh]
Si
63
-E-vinylsilane
Si
64
H
[Rh]
Si
H
[Rh]
-Z-vinylsilane
Scheme2.8 Rationalisation of the selectivity observed in the hydrosilylation of alkynes by the

complexes 61 and 62
Nickel complexes formed in situ by the reaction of Ni(1,5-COD)2 with the imidazolium salts IMesHCl or IPrHCl in the presence KOtBu catalyse the hydrosilylation
of internal or terminal alkynes with Et3SiH. Interestingly, Ni tri-butylphosphine
complexes are inactive in this hydrosilylation reaction. The monosilylated addition
products were obtained with slow addition rates of the alkyne in the reaction mixture
and were formed with variable degree of stereoselectivity, depending on the type of
the alkyne, the silane and the ligand on Ni [50].
The catalytic hydrosi(ly)lations of other C=X functional groups (X = O, NR)
constitute alternative routes to the reduction of aldehydes, ketones, imines and other
carbonyl compounds (Scheme2.9), circumventing the use of molecular hydrogen or
occasionally harsh transfer hydrogenation conditions.
O
R
SiR'3H
catalyst
SiR'3
H
R
Y
Y = alkyl, aryl, H, OR
Y
Scheme2.9 Hydrosilylation of carbonyl compounds to silyl ethers
The hydrosilylation of carbonyl compounds by Et3SiH catalysed by the copper

NHC complexes 65 and 6667 constitutes a convenient method for the direct synthesis
of silyl-protected alcohols (silyl ethers). The catalysts can be generated in situ from the
corresponding imidazolium salts, base and CuCl or [Cu(MeCN)4]X, respectively. The
catalytic reactions usually occur at room temperature in THF with very good conversions and exhibit good functional group tolerance. Complex 66, which is more active
than 65, allows the reactions to be run under lower silane loadings and is preferred for
the hydrosilylation of hindered ketones. The wide scope of application of the copper
catalyst [dialkyl-, arylalkyl-ketones, aldehydes (even enolisable) and esters] is evident
from some examples compiled in Table2.3 [5153].
(CH2)5
(CH2)5
(CH2)5
Me
Ph
Ph
Ph
i
Pr
p-tolyl
C6H11
Benzyl
Et
Me
Me
Me
i
Pr
H
H
OEt
IPrHBF4/CuCl
65
66
IPrHBF4/CuCl
IPrHBF4/CuCl
65
66
66
66
66
66
HSiEt3 (5:1)
HSiEt3 (3:1)
HSiEt3 (2:1)
HSiEt3 (5:1)
HSiEt3 (5:1)
HSiEt3 (3:1)
HSiEt3 (2:1)
HSiEt3 (2:1)
HSiEt3 (2:1)
HSiEt3 (2:1)
HSiEt3 (2:1)
NaOtBu (20%)
NaOtBu (612%)
NaOtBu (12%)
NaOtBu (20%)
NaOtBu (20%)
NaOtBu (612%)
NaOtBu (12%)
NaOtBu (12%)
NaOtBu (12%)
NaOtBu (12%)
NaOtBu (12%)
Table2.3 Selected data for the hydrosilylation of R1YC=O, R1 = alkyl, phenyl, Y = alkyl, H or OEt
R1
Y
Catalyst (3 mol%)
Silane (Si:substrate)
Base (mol%)
T (C)
rt
rt
rt
rt
rt
rt
rt
rt
rt
rt
55
t (h)
2
0.75
0.5
4
3
3
4
0.3
0.3
0.6
6
Conv. (%)
99
100
95
96
99
98
98
94
92
70
69
Ref
[33]
[33]
[32]
[33]
[33]
[33]
[32]
[32]
[32]
[32]
[32]
36
A. A. Danopoulos
37
The proposed mechanism of the catalytic reaction involves the formation of the
Cu(I) alkoxide 68 by displacement of either the chloride or the NHC from 6567,
followed by conversion to the hydride 69 by metathetical exchange of the tertbutoxide by the H of the silane (Fig.2.10).
i Pr
i Pr
i Pr
i Pr
i Pr
Cu
Pr
Pr
Pr
i Pr
+
Cu
i Pr
Cl
X
i Pr
65
i Pr
66 X = BF4
67 X = PF6
Fig.2.10 Hydrosilylation catalysts of carbonyl compounds based on Cu-NHC complexes
Transfer of the hydride from the Cu to the electrophilic carbon and cleavage of
the copper alkoxide by the silane regenerates 69. Recent reports point to the influence of the type of the counter ion X of the homoleptic 6667 on the activity, the
BF4 being superior to the PF6 analogue; this effect has been attributed to differences in the rate of active catalyst generation from the homoleptic [Cu(NHC)2]+X
and NaOtBu due to solubility differences of the inorganic salts formed during the
displacement of the NHC by tBuO [54] (Scheme2.10).
i Pr
i Pr
N
Cu
Pr
i Pr
i Pr
R3SiH
i Pr
Pr
i Pr
Cu
Ot Bu
68
H
69
Scheme2.10 Intermediates in the Cu-catalysed hydrosilylation of carbonyl compounds
The Rh-catalysed asymmetric hydrosilylation of prochiral ketones has been

studied with complexes bearing monodentate or heteroatom functionalised NHC
ligands. For example, complexes of the type [RhCl(1,5-cod)(NHC)] and [RhL(1,5cod)(NHC)][SbF6], 70, where L = isoquinoline, 3,5-lutidine and NHC are the
chiral monodentate ligands 71 (Fig.2.11).
1(0)+
R
(Cl)L
N
Rh
70
Ph
Ph
R
N
R
N + N
R
Ph
Ph
71
N
N
Rh Br
R'
Cl
R = Me, i Pr
72 R = 2,6-i Pr-C6H2, R' = t Bu
73 R = Mes, R' = t Bu
Fig.2.11 Chiral ligand designs in Rh catalysts for the enantioselective hydrosilylation of carbonyl
compounds
38
A. A. Danopoulos
X-ray crystallography and variable temperature 1H NMR studies show that the
conformation of the coordinated imidazolidin-2-ylidene, in both the neutral and
cationic complexes 70, is anti, anti with respect to the Ph of the backbone of the
NHC, exclusively in the solid state and predominantly in solution at lower temperatures (75C). At room temperature in solution, possible conformer interconversion by the rotation around the phenyl-N bond of the NHC substituent is
apparent from the broadness of the peaks in the NMR spectra. Hydrosilylation of
acetophenone by Ph2SiH2 catalysed by 70 at room temperature or at 20C results
in maximum ee of 58%. However, at lower temperatures the reaction rates are
much slower [55].
NHC complexes of Rh functionalised with chiral oxazoline ligands, for example
72 and 73, have been developed as pre-catalysts for the enantioselective hydrosilylation of ketones. After abstraction of the Br from 7273 with silver reagents, the
cationic complexes obtained were employed for the hydrosilylation of prochiral
ketones with various silanes. The conversions and enantioselectivities observed
were dependent on the nature of the R and R groups of the ligand, the silane and
reaction conditions. Higher enantioselectivities for the hydrosilylation of acetophenone to 1-phenyl-ethanol were observed with bulky silanes [Ph2SiH2, ( p-tolyl)2SiH2]
at the optimum temperature (60C); both higher or lower temperatures had a detrimental effect on the ee observed. This nonlinear temperature dependence of the
ee has been interpreted by assuming two enantioselectivity determining steps in the
catalytic reaction, one possibly involving the reversible coordination of the prochiral ketone onto Rh and the other the migratory insertion of the coordinated ketone
into the RhSi bond, that can become rate-determining. Under optimised conditions
acetophenone was reduced at 92% yield, with very good ee (90%), while other
methyl-n-alkyl ketones were reduced at good asymmetric induction (6580% ee)
depending on the ketone [56]. Interestingly, introduction of a methylene spacer
between the NHC and the chiral oxazoline in 7273 results in catalysts that show
disappointing chiral induction [57].
2.5Hydroboration and Diboration Reactions

The metal catalysed hydroboration and diboration of alkenes and alkynes (addition
of HB and BB bonds, respectively) gives rise to alkyl- or alkenyl-boronate or
diboronate esters, which are important intermediates for further catalytic transformations, or can be converted to useful organic compounds by established stoichiometric methodologies. The syn-diboration of alkynes catalysed by Pt phosphine
complexes is well-established [58]. However, in alkene diborations, challenging
problems of chemo- and stereo-selectivity control still need to be solved, with the
most successful current systems being based on Pt, Rh and Au complexes [5961].
There have been some recent advances in the area by using NHC complexes of Ir,
Pd, Pt, Cu, Ag and Au as catalysts under mild conditions, which present important
advantages in terms of activity and selectivity over the established catalysts.
39
The Ag complex 74 catalyses the diboration of internal and terminal alkenes to

1,2-bis-diboronate esters by bis(catecholato)diboron, (Bcat)2, in THF at room temperature. Variable conversions (3090%) were obtained at 5 mol% loading after 60 h.
Terminal alkenes with electron-rich substituents (Ph, Cy) gave the highest conversions. This reaction represents the first example of a Ag-NHC complex catalysed
reaction. The choice of silver was rationalised based on the mechanism of diboration,
which involves the insertion of the electron rich metal centre into the BB bond, followed by the alkene insertion and the release of the mono- or di-boronated organic
products. The electron rich AgI with low energy d orbitals minimises p-alkene bonding and, therefore, b-H elimination is suppressed, resulting in inhibition of vinyl
boronates formation. It is interesting to note that although 74 is chiral, it does not
induce any enantioselectivity in the diboration reactions of prochiral substrates [62].
Ag
N
R
N
N
Cl
Ag R
R=
Ph
N
N
AgCl
77
R
R
75 M = Ag, R = nBu, X = AgCl2
n
76 M = Au, R = Bu, X = Cl
Cl
74 M = Ag, X = AgCl2
Ph
+
M
X
X
Bu
Y N
N
Pt
n Bu
Si
Si
78 Y = N, X = H
79 Y = CH, X = H
80 Y = CH, X = Cl
Fig.2.12 Silver, gold and platinum complexes with monodentate NHC ligands as catalysts for
the diboration of alkenes and alkynes
Diboration of terminal alkenes has also been studied with other d10 metals
(Fig. 2.12) including the AgI and AuI complexes 7577 and the Pt0 complexes
7879. Styrene is diborylated with 100% selectivity and good conversions in THF
(46% for 75 and 94% for 77 at 5 mol%, 60 h) using equimolecular amounts of
(Bcat)2. The difference in activity between the Ag and Au complexes has been
ascribed to the increased lability of the AgNHC bond, which may lead to catalyst
decomposition under the reaction conditions. In both catalytic systems it is believed
that the active species involves only one coordinated NHC ligand. Complex 77 is
less active than 74 and 75, possibly due to steric reasons. The enantioselectivity of
77 in the diboration of prochiral alkenes is very low [63].
Diboration of terminal and internal alkynes by (Bcat)2 [B(cat)2:alkene = 1:1] was
also achieved by using complexes 78 and 79 at room temperature in THF. Best activity was observed with 78 containing the less electron donating triazolylidene carbene
ligand. Terminal alkenes can also be diborylated under the same conditions, however
the selectivity for the diborylated product was much lower (up to 65%) [64].
The palladium (II) NHC complexes 81 and 82 (Fig.2.13) have also been used
as catalysts in the diboration of styrene. In the presence of NaOOCCH3, (1 equiv.,
40
A. A. Danopoulos
5 mol% catalyst, in THF at rt), excellent conversions were obtained when (Bcat)2
was the boron source. Selectivities were also high for the diborylated product when
excess of (Bcat)2 was used [(Bcat)2:styrene 3:1]. Other terminal and internal
alkenes were also diborylated in high yields and selectivities under the same conditions. A mechanism involving metathetical PdB bond formation (without change
of the oxidation state) may be operating. However, an involvement of PdII/PdIV
species, formed by oxidative addition of BB to a cationic PdII and formation of an
NHC stabilised PdIV-boryl complex, is also plausible. In the presence of base
(NaOAc), the mechanism could involve transmetallation, and in this case interaction of the boron entering group with the base giving borate species may increase
its nucleophilicity and facilitate the PdB(cat) bond formation. DFT and in situ
11
B NMR experiments support these mechanistic models [65].
N
N
N
N
+
Pd
N
Br
81
Br
N
N
Pd
82
N
I
Ir Cl
N
N
83
Fig.2.13 Diboration catalysts based on palladium and iridium NHC complexes
The Ir complexes 83 or [Ir(IMes)Cl2Cp*], in the presence of NaOAc and excess

of (Bcat)2, catalyse the diboration of styrene, at high conversions and selectivities for
the diborated species, under mild conditions. Other terminal alkenes react similarly.
The base is believed to assist the heterolytic cleavage of the (cat)BB(cat) bond and
the formation of IrB(cat) species, without the need of BB oxidative addition [66].
The stoichiometric insertion of terminal alkenes into the CuB bond of the
(NHC)CuB(cat) complex, and the isolation and full characterisation of the b-boryl
alkyl-copper (I) complex has been reported. The alkyl complex decomposes at
higher temperatures by b-H elimination to vinylboronate ester [67]. These data
provide experimental evidence for a mechanism involving insertion of alkenes into
Cuboryl bonds, and establish a versatile and inexpensive catalytic system of wide
scope for the diboration of alkenes and alkynes based on copper.
The complexes [Cu(NHC)(MeCN)][BF4], NHC = IPr, SIPr, IMes, catalyse the
diboration of styrene with (Bcat)2 in high conversions (5 mol%, THF, rt or reflux).
The (Bcat)2/styrene ratio has also an important effect on chemoselectivity (monoversus di-substituted borylated species). Use of equimolecular ratios or excess of
B(cat)2 results in the diborylated product, while higher alkene:B(cat)2 ratios lead
selectively to mono-borylated species. Alkynes (phenylacetylene, diphenylacetylene) are converted selectively (9095%) to the cis-di-borylated products under the
same conditions. The mechanism of the reaction possibly involves s-bond metathetical reactions, but no oxidative addition at the copper. This mechanistic model
was supported by DFT calculations [68].
Platinum mediated regioselective HB addition of HB(cat) to vinyl arenes and
alkynes has been realised using the complexes 79 and 80 (Fig. 2.12). The reactions
41
with vinyl arenes proceed at rt in THF (0.05 mol%) giving high conversions (80100%)
of mixtures of alkyl or alkenyl boranes, with predominantly branched product
(7090%). Interestingly, the activity of the catalytic system is maintained days after the
completion of the reaction, while addition of PPh3 into the catalytically active system
retards or deactivates it. Aryl alkynes are hydroborated selectively to the mono-borylated product, with higher selectivity to the linear alkenyl borane. The addition of aryl
iodides into the catalytic system results in the cross coupling of the in situ formed
alkenyl boranes with the aryliodide in one pot, giving alkenyl arenes [69].
In an attempt to study the electronic effects of the substituents in the four- and
five-positions of the coordinated imidazol-2-ylidene on the MCNHC bonding, and
the related catalytic reactivity, the complexes [RhCl(1,5-COD)(NHC)], where NHC
is imidazol-2-ylidene substituted in the four- or five-positions with the s- or
p-electron withdrawing groups CF3, Cl, NO2 and CN, were used as catalysts
in the hydroboration of alkynes with HB(pin). In the hydroboration of phenylacetylene, it was found that complexes with ligands bearing p-electron withdrawing
groups in the four- and/or five-position of the imidazolylidene, were affording
lower yields of products than the ones with s-electron withdrawing groups. These
data have been interpreted as an indication that p-interactions between the coordinated NHC with a metal exist, a fact that was disputed in the early era of the NHC
ligand development, and may have important implications in catalyst design [70].
However, in the hydroboration of 1-octyne no effect was observed.
Hydroboration of acyclic and cyclic aryl alkenes with (Bpin)2 (1.1 equiv.) in the
presence of NaOtBu (1100 mol%) and MeOH (2 equiv.) is catalysed by
[CuCl(NHC)], (0.55 mol%) NHC = IMes, SIMes and ICy, and proceeds with very
good conversions and regioselectivity (Scheme2.11).
Me
Me
[CuCl(NHC)]
(Bpin) 2, NaO tBu, MeOH
B(pin)
Scheme2.11 Hydroboration of arylalkenes catalysed by copper NHC complexes
This regioselectivity is opposite to the one observed by the non-catalysed additions of BH3THF or 9BBN to the same alkene, or those catalysed by Rh and Ir
catalysts. Chiral NHC ligands (generated from 84) on Cu under the same conditions
proceed with high enantioselectivity (enantiomeric ratio 99:1) [71] (Scheme2.12).
Me CuCl (7.5 mol%), KOtBu (30 mol%) 84
(Bpin)2 (1.1eq), MeOH, THF,-50oC, 48 h
Ph
Ph
N + N
SO3
84
Me
B(pin)
99:1 er
i Pr
Pr
i Pr
Scheme2.12 Enantioselective hydroboration of arylalkenes catalysed by copper NHC complexes
42
A. A. Danopoulos
2.6Hydroamination Reactions
Intermolecular and intramolecular hydroamination of alkenes and alkynes is an atom
economical method for the synthesis of a range of acyclic and cyclic alk(en)ylamines
from simpler amine precursors. The reaction can be catalysed by either electropositive
(main group metals, early transition metals and lanthanides-actinides) or late transition
metals, under different mechanistic regimes. The relatively facile intramolecular
hydroamination of alkynes and allenes is more ubiquitous and commonly studied.
Intermolecular hydroamination of alkenes is more challenging and examples with
activated, electron-deficient alkenes have recently appeared. Control of regioselectivity
(Markovnikov, anti-Markovnikov) and suppression of competing side-reactions (alkene isomerisation, oligomerisation, etc.) in addition to high activity, especially when
expensive late transition metals are used as catalysts, are important features of the catalyst development [72, 73]. NHC complexes with both electropositive and late transition metals have been studied as alkene and alkyne hydroamination catalysts.
A catalytic system comprising Ti(NMe2)4, LiN(SiMe3)2 and IMes has been
developed for the intermolecular hydroamination of terminal aliphatic alkynes
(1-hexyne, 1-octyne, etc.) with anilines [toluene, 100C, 10 mol% Ti(NMe2)4].
Markovnikov products were dominant. Substituted anilines reacted similarly. High
conversions (8595%) were observed with specific anilines. The optimum Ti/IMes/
LiN(SiMe3)2 ratio was 1:2:1. However, the nature of the active species and especially the role of LiN(SiMe3)2 are unclear [74].
The Rh and Ir complexes 8588 (Fig.2.14) have been tested for the intramolecular
hydroamination/cyclisation of 4-pentyn-1-amine to 2-methyl-1-pyrroline (n = 1). The
reactions were carried out at 60C (11.5 mol%) in THF or CDCl3. The analogous
rhodium systems were more active. Furthermore, the activity of 87 is higher than 85
under the same conditions, which was attributed to the hemilability of the P donor in the
former complex, or to differences in the trans-effects of the phosphine and NHC ligands,
which may increase the lability of the coordinated CO in the pre-catalyst [75, 76].
( )n
C C H
catalyst
( )n
N
NH2
N
N
OC
N
+
Rh
CO
85 A = BF4
86 A = BPh4
Ph
BPh4
+ P
Ph
M
OC CO
87 M = Rh
88 M = Ir
N
N
I
nBu
N
M
2
N
n Bu
89 M = Rh
90 M = Ir
Fig.2.14 Rhodium and iridium catalysts for the intramolecular hydroamination of alkynes
The pincer complexes 8990 (Fig.2.14) catalyse the intramolecular hydroamination/

cyclisation of unactivated alkenes, yielding pyrrolidines and piperidines (n = 1, 2,
respectively). The reactions can be carried out in benzene or water with high
43
conversions (>95% at 2.5 mol% at 110C, overnight). Rh and Ir catalysts show very
similar activity without competing alkene isomerisation. Interestingly, no reaction
was observed with primary amines. The reaction mechanism may involve metalamido bond formation followed by alkene insertion and reductive elimination, or
p-coordination of the alkene followed by nucleophilic attack on the activated coordinated alkene [77, 78].
Hydroamination of activated alkenes has been reported with complexes 9193
(Fig.2.15). For example, 91 catalyses the hydroamination of methacrylonitrile (X =
CN in Scheme2.13) by a range of secondary amines (morpholine, thiomorpholine,
piperidine, N-methylpiperazine or aniline) in good to excellent conversions (67
99%) and anti-Markovnikov regioselectivity (5 mol%, 80C or rt, 2472 h). Low
enantioselectivies were induced (ee 3050%) depending on the amine used and the
reaction temperature [79].
Fe
N
Fe
P
Ph2
N
2+
Pd
PPh2
2PF6
NCMe
HN
2BF4
N tBu
2+
Pd NCMe
t
N Bu
91
2BF4
N Mes
2+
HN MeCN Pd NCMe
N
N Mes
N
93
92
Fig.2.15 Hydroamination catalysts based on palladium NHC complexes
Complexes 92 and 93 also show good activity for the hydroamination of methacrylonitrile with morpholine, piperidine or N-methylpiperazine (7093% conversion at
2.5 mol%, 90C in 24 h) [80].
N
X
+
N H
Scheme2.13 Intermolecular hydroamination of activated alkenes

i Pr
i Pr
N
Cu
i Pr
Pr
NHR 94 R = Ph
95 R = CH2Ph
Fig. 2.16 Copper-amido complexes as catalysts for the intermolecular hydroamination of

electron-deficient alkenes
The well-defined copper complexes 94 and 95 (Fig. 2.16) have been used as
catalysts for the intermolecular hydroamination of electron-deficient alkenes
[Michael acceptors, X=CN, C(=O)Me, C(=O)(OMe)] and vinyl arenes substituted
44
A. A. Danopoulos
by the electron-withdrawing groups NO2 CN, CF3 but not Cl, Br or H

(Schemes2.13 and 2.14).
Cu-catalyst
5 eq. PhNH2, C6D6, 80-120oC
X
NHPh
X = NO2, CN, CF3
Scheme2.14 Copper-catalysed intermolecular hydroamination of electron-deficient aryl alkenes
The hydroaminations of electron-deficient alkenes with aniline or small primary

alkylamines proceed at high conversions (8595%, under mild conditions, 5 mol%,
rt), giving exclusively the anti-Markovnikov addition product. Secondary dialkyl or
bulky primary amines require longer reaction times. With amines containing
b-hydrogens, no imine side-products were observed.
The proposed reaction mechanism involves intermolecular nucleophilic addition
of the amido ligand to the olefin to produce a zwitterionic intermediate, followed by
proton transfer to form a new copper amido complex. Reaction with additional amine
(presumably via coordination to Cu) yields the hydroamination product and regenerates the original copper catalyst (Scheme2.15). In addition to the NHC complexes 94
and 95, copper amido complexes with the chelating diphosphine 1,2-bis-(di-tertbutylphosphino)-ethane also catalyse the reaction [81, 82].
RHN
[Cu] N
R
H
RNH2
R
[Cu] N
X
H
R
X
[Cu] N
+ H
Scheme2.15 Postulated mechanism for the copper-catalysed hydroamination of electron-deficient

alkenes
Finally, intramolecular hydroamination/cyclisation of N-alkenyl ureas was catalysed

by the well-defined [AuCl(IPr)] complex (Scheme2.16), in the presence of AgOTf (5
mol%, rt, methanol, 22 h). The cationic Au(IPr)+ is presumably the active species [83].
O
i Pr
N
H
NHPh
[AuCl(NHC)] (5 mol%)
AgOTf (5 mol%), MeOH
i Pr
O
NHPh
Me
Scheme2.16 Gold-catalysed intramolecular hydroamination of alkenes
45
2.7Hydrothiolation, Hydroalkoxylation
and Hydroaryloxylation Reactions
Hydrothiolations (addition of HSR across the CC multiple bond) of alkynes,
electron-deficient alkenes and electron-deficient vinyl arenes have been catalysed
by NHC complexes of Ni and Cu, respectively [Scheme2.17a-c].
R +
SH
Cat. 1 mol%
NEt3, 80oC, 5 h
R
X
RS
X
+ RS H
RS-H
isomerisation
S
(a)
(b)
(c)
SR
X = NO2, CN, CF3
Scheme2.17 Product formation in the hydrothiolation of alkynes and alkenes
The hydrothiolation of terminal alkyl alkynes with 96 (Fig.2.17) proceeds with

good degree of regio- and chemo-selectivity, especially with thiophenol and
p-methoxy-thiophenol as substrates. Isomerisation to the internal alkenyl thiolates
accounts for less than 9% of the thiolated products under the reaction conditions.
In addition, further hydrothiolation of the vinyl thioether product is not observed.
Typical conversions of 7085% at 1 mol% loading at 80C within 5 h are observed.
Arylthiols substituted with electron-withdrawing groups afford lower conversions.
The thiolato complex 97 that was postulated as the active catalytic species in the
reaction was prepared from 96 and the thiol in the presence of NEt3. Certain analogues of 97 (NHC = IMes, SIMes, IPr, SIPr; R = Ph) have also been independently
synthesised, isolated and fully characterised. A plausible mechanism for the hydrothiolation involves insertion of the alkyne into the NiSR bond forming the (non-isolable)
b-thioalkenyl complex, from which the product can be released via alkanolysis of the
NiC bond by the thiol and regeneration of the active catalyst 97 [84].
iPr
Ni
NHC
iPr
Ni
Cl
NHC
96 NHC = IMes
SR
97
N
Cu
iPr
iPr
SR
98 R = Ph
99 R = CH2Ph
Fig.2.17 Nickel and copper complexes as catalysts for the hydrothiolation of alkynes and
activated alkenes
The hydrothiolation of electron-deficient alkenes [X = CN, C(=O)(OMe)]

and p-nitro-styrene was catalysed by the CuI complexes 98 and 99. The reactions
with phenyl- or benzyl-thiol proceed with high conversions (>90%, rt, 5 mol%).
46
A. A. Danopoulos
Anti-Markovnikov products are only observed. The postulated mechanism for

these reactions is analogous to the previously discussed for the copper-catalysed
hydroamination (Scheme 2.15) with the coordinated thiolate (rather than the
amide) acting as nucleophile [82, 85].
Hydroalkoxylation and hydroaryloxylation (addition of HOR and HOAr,
respectively, across the CC multiple bonds) of electron-deficient alkenes, by alcohols
or phenols was studied in the presence of [Cu(OR)(NHC)], NHC = IPr, R = OEt,
100; NHC = IPr, R = OPh, 101; NHC = SIPr, R = OEt, 102; NHC = SIPr, R = OPh,
103; NHC = IMes, R = OPh, 104], as well-defined catalysts. In general, the addition
of alcohols to the alkenes is slower than the addition of amines. For the addition of
ethanol, highest activities are observed with 100 (conversion of acrylonitrile or
methyl vinyl ketone with ethanol >95% after 12 h and 5 min, respectively, at rt, 5
mol%). For the addition of phenol to acrylonitrile the most efficient catalyst is 104.
In attempted hydroalkoxylations of methylacrylate with ethanol catalysed by
the copper ethoxides 100 or 102, copper-catalysed transesterification to the
ethylacrylate was observed instead of the addition reaction [81].
Intermolecular hydroalkoxylation of 1,1- and 1,3-di-substituted, tri-substituted
and tetra-substituted allenes with a range of primary and secondary alcohols,
methanol, phenol and propionic acid was catalysed by the system [AuCl(IPr)]/
AgOTf (1:1, 5 mol% each component) at room temperature in toluene, giving
excellent conversions to the allylic ethers. Hydroalkoxylation of monosubstituted
or trisubstituted allenes led to the selective addition of the alcohol to the less hindered allene terminus and the formation of allylic ethers. A plausible mechanism
involves the reaction of the in situ formed cationic (IPr)Au+ with the substituted
allene to form the p-allenyl complex 105, which after nucleophilic attack of the
alcohol gives the s-alkenyl complex 106, which, in turn, is converted to the
product by protonolysis and concomitant regeneration of the cationic active
species (IPr)-Au+ (Scheme2.18) [86].
R
R
R'
R'
AuL+
105
R"OH
OR" R
R'
OR" R
H+
H+
R'
AuL
106
Scheme2.18 Postulated mechanism for the Au-NHC catalysed hydroalkoxylation of allenes
47
2.8Hydration Reactions
The hydration of alkynes to ketones, catalysed by [AuCl(IPr)]/AgSbF6 in 1,4-dioxane/H2O (2:1) or methanol has been studied in detail. The reaction proceeds
at surprisingly low catalyst loadings (501,000 ppm), especially, for terminal
alkynes in methanol, and is extremely sensitive to the nature of the catalyst, the
silver activator and the reaction conditions. The best activity is obtained with the
IPr ligand on Au, while silver salts with anions other than [SbF6], either reduce
the conversion or result in catalytically inactive species. Interestingly, diphenylacetylene is hydrated faster in 1,4-dioxane than methanol, the reverse behaviour
being observed for the terminal phenylacetylene. This feature may imply that two
different reaction mechanisms may be operating in dioxane and methanol, with
methanol being a non-innocent solvent. This proposition is also supported by the
detection of vinyl methylether intermediates, resulting from the direct addition of
methanol to the alkyne, which in turn converts to the final ketone product. The
nature of the catalytic species involved in this reaction is not known, but may
involve solvated, hydroxo- or alkoxo-gold complexes (NHC)Au(solvent)+, (NHC)
Au(OH), (NHC)Au(OR). The AuNHC based catalytic system described here is
much more active than the previously known phosphine analogue, [AuMe(PPh3)]
which requires the use of strong acids (H2SO4, CF3SO3H, etc.) for catalyst activation [87, 88].
The intermolecular hydration of allenes catalysed by [AuCl(IPr)]/AgOTf
(1:1, 5 mol%) in dioxane/water at room temperature, has also been studied. In most
cases, low to modest yields (2565%) of E-allylic alcohols were obtained by selective addition of the water to the terminal C atom of the allene group [89].
2.9Hydroarylation Reactions
Hydroarylation, (addition of HAr, Ar = aryl), of alkynes, catalysed by Pd(OOCCH3)2
or Pd(OOCCF3)2 in acetic acid, is an atom-economic reaction, giving rise to substituted cis-stilbenes (Fujiwara reaction). Catalytic conversions and improved
chemoselectivity to the mono-coupled product under mild conditions can be
achieved by modification of the metal coordination sphere with NHC ligands.
Hydroarylation of mesitylene by ethylpropiolate (Scheme2.19) catalysed by complex 107 (Fig. 2.18) proceeds in good conversions (8099%, 1 mol%) under mild
conditions at room temperature.
COOEt
+
COOEt
+
COOEt
Scheme2.19 Products from the hydroarylation reactions of activated alkynes
COOEt
48
A. A. Danopoulos
Surprisingly, the organometallic catalyst shows good stability under the reaction
conditions (CF3COOH/CH2Cl2). In the absence of 107 (Fig.2.18), Pd(OAc)2 under
the same conditions catalyses the same reaction with reduced activity (ca. 50%
conversion in 24 h) and different chemoselectivity. Arenes, substituted by electronwithdrawing substituents react slower. Both internal and terminal alkynes undergo
the reaction, however, the former require more forcing conditions [90].
iPr
iPr
N
Pd
N
iPr
iPr
CH3
Cl
OOCCH3
107
N
N
Cl
108 M = Pd
109 M = Pt
Fig.2.18 Palladium and platinum NHC complexes as catalysts in hydroarylations of alkynes
High activities and selectivities for the Z-monoarylated stilbene were also
obtained by the intermolecular hydroarylation of pentamethylbenezene by ethylpropiolate in CF3COOH/1,2-C2H4Cl2 (1:4) catalysed by 108 (0.1 mol%, 80C, 95%
in 7 h). NHC ligands with bulkier substituents on the NHC show higher activity.
The mechanism operating in this transformation has not been fully elucidated, but
there are indications that during the reaction the NHC ligand of 108 remains bidentate. Encouraging results were also obtained when using the Pt analogue 109 as
catalyst in hydroarylation reactions [91].
The intramolecular hydroarylation/cyclisation of aryl propargylic acetates
catalysed by the system [AuCl(IPr)]/AgBF4 (1:1, 2 mol%, 7292%, rt, 5 min) was
developed as a versatile and efficient method leading to indene derivatives 110
(Scheme2.20). Analogous catalytic systems, where the IPr was substituted by PPh3,
gave lower conversions and chemo-/regio-selectivity.
OAc
OAc
Cat.
R
+
AcO R
110 (major)
111
112
OAc
Scheme2.20 The synthesis of substituted indenes by intramolecular hydroarylation of aryl propargylic acetates
The postulated mechanism for the reaction involves activation of the alkyne by
p-coordination to the cationic (IPr)Au+, followed by direct nucleophilic attack by the
electron-rich aromatic ring to form product 111. Alternatively, two 1, 2-acetate migrations give the activated allene complex, which can be cyclised to product 110 by
nucleophilic attack of the aromatic ring on the activated allene (Scheme2.21) [92].
49

OAc
OAc
Au(IPr)
OAc
R
1,2 acetate
migration
111 R
OAc 1,2 acetate

migration
(IPr)Au
OAc
(IPr)Au R
AcO R
110 (major)
Scheme2.21 Postulated mechanism for the synthesis of substituted indenes by intramolecular

hydroarylation of propargylic acetates
2.10Allylic Alkylations and Other Substitution Reactions

Allylic substitutions catalysed by palladium NHC complexes have been studied
and the activity and selectivity of the catalysts compared to analogous Pd phosphine complexes. A simple catalytic system involves the generation of a Pd(NHC)
catalyst in situ in THF, from Pd2(dba)3, imidazolium salt and Cs2CO3. This system
showed very good activities for the substitution of the allylic acetates by the soft
nucleophilic sodium dimethyl malonate (2.5 mol% Pd2(dba)3, 5 mol% IPrHCl,
0.1 equiv. Cs2(CO3)2, THF, 50C) (Scheme 2.22). Generation of the malonate
nucleophile can also be carried out in situ from the dimethylmalonate pro-nucleophile, in which case excess (2.1 equivalents) of Cs2CO3 was used. The nature of the
catalytic species, especially the number of IPr ligands on the metal is not clear.
OAc
Ph
Ph
Pd2(dba)3, imidazolium salt, Cs2CO3

CH2(COOMe)2, base
CH(COOMe)2
Ph
Ph
Scheme2.22 Palladium-NHC complex catalysed substitution of allylic acetate by malonate
The substitution proceeds with retention of configuration at the substituted C atom

as confirmed by the reaction of suitable isomeric acetates. Retention of configuration
has also been observed in analogous Pd-phosphine catalysed reactions [93].
Compared to the Pd phosphine catalysts, the Pd/IPr system showed reduced reactivity, operating at higher reaction temperatures. Allylic carbonates, as well as harder
nitrogen nucleophiles, such as amine or sulfonamides, were unreactive [94].
A detailed comparative study of the allylic substitution in allylacetates by amines has
been carried out for the two related mixed donor ligand systems 113 and 114 shown in
Fig.2.19. The PC system shows dramatically lower activity than NP, which has been
attributed to the decreased electrophilicity of the coordinated allyl group, originating
from the strongly s-donating NHC and P donors, compared to N and P donors.
50
A. A. Danopoulos
R"
N
N
P Pd
Ph2
Fe
N
+
R"
R'
Fe
N N
Pd+
R'
P
Ph2
R
114
113
t
R" = Me, Bu
+
Pd
N
+
P
Ph2
115
Fig.2.19 Allylic substitutions with mixed donor Pd complexes
Enantioselectivity (which is linked to the regioselectivity of the attack of the nucleophile to the coordinated allyl) in the allylic amination of 1,3-diphenyl-allyl ethyl carbonate was also very low compared to the PN system. This was attributed to the
comparable trans-influence of P and NHC functionalities, leading to poor regioselection of the two allyl termini trans to the P and NHC ligands by the nucleophile [95].
Allylic alkylation of 3-acetoxy-1,3-diphenylpropene by sodium dimethylmalonate,
catalysed by the Pd-allyl complex 115, bearing the non-symmetric phosphonium ylide
NHC ligand (5 mol%), proceeds to completion with 100% regioselectivity.
Asymmetric allylic alkylation (AAA) has been studied using a variety of novel ligand
designs containing one NHC functionality and, usually, a classical heteroatom donor. In
addition to the work mentioned earlier with ferrocenylphosphine-functionalised NHC
complexes of Pd (113), the complexes 116119 (Fig.2.20) promote enantioselectivity in
AAA reactions. A family of complexes 116 was found to induce up to 90% enantioselectivity in AAA, especially with the more rigid analogues. The nature of the NHC group
has an important influence on the stereochemical outcome of the reaction [96]. The
AAA of E-1,3-diphenylprop-3-en-1-yl acetate by sodium malonate catalysed by a class
of imine functionalised NHC complexes 117 gave excellent conversions and enantioselectivities, with ee up to 92% in one case. The synthesis of the chiral bidentate ligand
uses commercially available chiral trans-1,2-diamino-cyclohexane [97].
R R'
N
+ S
Pd
116
Ph
Ph
N
Cy
Pd
Cl
117
Cl
R
O
+ N
Mes N
P
O
N
P
Ph
N
120
N
118 R = alkyl, phenyl
Ph
119 R = 2-(3,5-xylyl)-C6H4
Fig.2.20 Chiral Pd-NHC catalysts and ligands used for the asymmetric allylic alkylation
A comparative study of the AAA of E-1,3-diphenylprop-3-en-1-yl acetate by

sodium malonate using the chiral phosphine ligands 118119 showed that better ee
were observed if the phosphine ligands were combined with a monodentate NHC.
Best enantioselectivities were obtained in a catalytic system generated from [Pd(allyl)
(m-Cl)]2 and 119/IMes, indicating a synergistic effect of the NHC and phosphine on
the enantioselectivity of the reaction. The bidentate 120 showed also this synergism
but not as pronounced as the combination of the two monodentate ligands [98].
51
The Ag complex 121 in the presence of CuCl22H2O or Cu(OTf)2C6H6 catalyses

the allylic alkylations of allyl phosphates by dialkylzinc reagents with high enantioselectivity (Scheme2.23). A copper complex 122 which is the precursor to the catalytic
species was also isolated and structurally characterised (Figs.2.21 and 2.22) [99].
R
R'
121 (1 mol%)
ZnR"2
CuCl2.2H2O
or
Cu(OTf) 2.C6H6
OPO(OEt)2
R" R
R'
Conv. >98%
ee 70-98%
Scheme2.23 Copper-catalysed enantioselective allylic alkylation of allylphosphates
Mes N
Mes N
Cl
O
O
Cl Cu
O
Ag
Cu
Ag
Mes
N
121
N Mes
122
Fig.2.21 Chiral binap-based catalysts or catalyst precursors for the enantioselective allylic alkylation of allylphosphates
Ph
Ph
Ph
Ph
Mes N
Mes N
Ph
O
ClCu
N
N Mes
Ph
123
Ph
Mes N
ClCu
Ag
O
O
Ag
N
Ph
Ph
O O
S
Ph
124
O
N
N Mes
Ph
Ag
Ag
N
O
Mes
S O
O
Ph
125
Fig. 2.22 Combination of chiral imidazolidin-2-ylidenes and biphenyl linkers in the chiral
catalysts or catalyst precursors for the asymmetric allylic alkylations
The disadvantage of using optically pure binaphthyl building blocks for the
synthesis of the NHC ligands in 121 and 122 was addressed by introducing on the
imidazolidin-2-ylidene backbone chirality originating from the easily available in
optically pure forms 1,2-diphenyl-1,2-diamino-ethane, in combination with racemic biphenyl- rather than optically pure binapthyl-NHC wingtips. The analogous
silver and copper complexes 123 and 124 (Fig. 2.22) were formed as single
atropoisomers, and catalysed the alkylation of allyl phosphates by dialkylzincs
giving excellent chemical yields and enantioselectivities [100].
52
A. A. Danopoulos
The AAA of allylphosphates by vinyl aluminium reagents generated in situ by

hydroalumination of terminal alkynes with DIBAL-H in situ has recently been
reported (Scheme2.24).
R
OPO(OEt) 2
DiBAL-H
R'
R"
R'
R"
Scheme2.24 Asymmetric allylic alkylation of allylphosphates by in situ generated vinyl Al reagents
The most active catalyst for this reaction is formed in situ from 125 (fig. 2.22),
in the presence of copper salts. Interestingly, high conversions and ee are only
observed with the precursor 125 but not 123 or 121 [101].
Allylic alkylations of cinnamyl carbonate by sodium malonate have been studied
with a series of ruthenium catalysts, obtained from the azolium salts 126128 and
the ruthenium complex 129 (Scheme 2.25) in MeCN or THF to give moderate
yields of mixtures of alkylated products in the allylic and ipso-carbons (90:10 to
65:35). The observed regioselectivity is inferior to similar ruthenium systems with
non-NHC co-ligands. The stereoelectronic factors which govern the observed regioselectivity were not apparent [102].
azolium salt
Ar
PF6 azolium salt

KOt Bu
NCMe
MeCN
NCMe
129
+
Ru
Ru catalyst
N
+
N Cl
Ar
Ar
N
+
N
N
+
N Cl
Ar
Ar
127
126
Ar = substituted aryl
Cl
Ar
128
Scheme2.25 Generation of ruthenium catalysts for the allylic alkylation of cinnamyl carbonate
A regioselective catalytic system for the allylic substitution of non-symmetric allyl

carbonates by carbon and nitrogen nucleophiles based on [nBu4N][Fe(NO)(CO)3] and
PPh3 was developed (Scheme 2.26). The high regioselectivity was ascribed to
the slow s-allyl- to p-allyl-isomerisation relative to the rate of substitution. However,
the use of high excess of the pro-nucleophile and DMF solvent are drawbacks
on the atom efficiency and functional group tolerance of the system.
O
tBuO
[Fe(CO) 3(NO)]/NHC (2.5 mol%)

i BuO C
2
i BuO
CO2i Bu
2C
CO2i Bu , 80oC
130
i BuO
2C
CO2iBu
131
Scheme2.26 Regioselective iron-catalysed allylic substitution of nonsymmetric allyl carbonates
53
Replacement of PPh3 by various NHC ligands, generated in situ, resulted in

higher conversions by using stoichiometric quantities of the C nucleophile.
However, a dependence of the ratio of the isomeric products 130 and 131 on the
nature of the NHC ligand was noticed. In general, the bulky SItBu favoured the
formation of 130, while with SIPr variable ratios of both 130 and 131 were
obtained, depending on the substituents of the allyl source and the nucleophilicity
of the nucleophile; stronger nucleophiles favoured the formation of 130. The
experimental results were rationalised by the assumption that substitution from the
initially formed s-allyl complex (leading to 130) is possible, either when bulky
SItBu is present, which disfavours s-allyl isomerisation via a p-allyl intermediate,
and/or when the high nucleophilicity entering group is present, resulting in a fast
substitution reaction. When SIPr ligands are used, a relatively fast isomerisation
process (s-, p-, s-allyl) competes with the direct substitution giving rise to substantial amounts of 131 (Scheme2.27) [103].
N
130
Nu
disfavoured
Fe
R
R
N
Fe
Fe
Nu
Fe
Fe
Nu
131
N
Fe
Nu
130
131
Scheme 2.27 Proposed mechanism to account for the observed regioselectivity in the allylic
alkylations catalysed by Fe-NHC complexes. Other co-ligands on Fe are omitted for clarity
In an interesting system, the reduced electrophilicity of the Pd-allyl complexes

with NHC ligands, mentioned previously, was exploited in order to promote stoichiometric and catalytic umpolung allylation reactions of benzaldehyde, by nucleophilic
attack of the coordinated allyl group (Scheme2.28). The best results were obtained
with the family of phosphine- or amine-functionalised NHC complexes [104].
Interestingly, [Pd(h3-C3H5)Cl(IMes)] complex does not react with aldehydes. It is
plausible that the nucleophilic h1-allyl Pd intermediate attacks the carbonyl carbon.
SnR3 +
O
R
132
H
OH
R
N
Pd
L = PPh2
pyridine
NiPr2
132
Scheme2.28 Allylation of benzaldehyde mediated by Pd-NHC complexes
54
A. A. Danopoulos
2.11Additions to Conjugated Enones and Related Reactions

The CuII (for example Cu(OTf)2) catalysed addition of dialkylzincs or Grignards to
a,b-unsaturated carbonyl compounds was found to be accelerated in the presence
of N-heterocyclic carbenes, generated in situ (especially the strongly s-donating
SIMes), or formed by transmetallation from Ag-carbene complexes to copper
(Scheme2.29). For the addition to cyclohex-2-enone, high conversions (>90%) at
low catalyst loading (25 mol%) were obtained at temperatures 20C to rt within
510 min [105]. The ligand acceleration was attributed to the stabilisation of a
putative CuIII transition state by the strongly s-donating NHC.
O
ZnR2 or RMgX, Cu(OTf) 2

NHC or Ag(NHC)X
Scheme2.29 Addition to ,-unsaturated carbonyls mediated by Cu-NHC complexes
Asymmetric versions of this transformation were also developed by using chiral

imidazolium pro-ligands as NHC precursors, or silver transmetallation methodology
with chiral NHC ligands (Fig.2.23) [106]. Imidazolium salts with chiral N-substituents
(132) or imidazolidinium salts with chirality at the backbone of the heterocycle (133)
gave quantitative conversions at 78C with good ee (58% and 70% respectively).
Improvement in the catalyst activities and enantioselectivities was realised by
the development of the chiral, bidentate alkoxy-functionalised imidazolium and
imidazolidinium pro-ligands (134 and 136). 134, after deprotonation, was used to
prepare the well-defined complex 135. Both 136 in the presence of BuLi and
Cu(OTf)2 or 135 without any additional co-reagents were efficient catalysts in the
asymmetric 1,4 addition of dialkylzincs and Grignards to cyclohexen-2-one giving
higher ee (83% at rt and 51% at 30C, respectively) [107, 108].
Ph
Ph
N + N
BF4
132
H
tBu
MeO
N + N
THF
Cl
135
Mes N
PF6
+ N
136
HO
t Bu
tBu
Cl OHH
134
OMe
AgCl
133
Cu
tBu
tBu
Ph
Ph
Et
N + N
Ph
Et
137
BF4
Fig. 2.23 Chiral NHC ligand precursors and complexes used in the asymmetric alkylation of
conjugated enones
Recently, attempts were made to replace the air- and moisture-sensitive zinc and
magnesium reagents in the copper-catalysed asymmetric conjugate addition, with
55
easier to handle air-stable carbosilanes. Aryl- or alkenyl-trifluorosilanes, in the

presence of the fluoride source tris(dimethylamino)sulfonium difluorotrimethylsilicate (TASF, generating in situ the nucleophilic aryl- or alkenyl-tetrafluorosilicates)
gave good to excellent yields (6397%) and ee (4797%) of the 1,4 addition products to cyclic enones. The catalysts were generated in situ from the imidazolium
salt, NaOtBu and CuBr at rt. In this study, evaluation of the efficiency of various
chiral (C2 and non-C2 symmetric) NHC-pro-ligands showed that the non-C2
analogue 137 gave the best yields and ee [109].
Asymmetric conjugate addition of dialkyl or diaryl zincs for the formation of all
carbon quaternary chiral centres was demonstrated by the combination of the chiral
123 and Cu(OTf)2C6H6 (2.5 mol% each component). Yields of 9498% and ee of
up to 93% were observed in some cases. Interestingly, the reactions with dialkyl
zincs proceed in the opposite enantioselective sense to the ones with diaryl zincs,
which has been rationalised by coordination of the opposite enantiofaces of the
prochiral enone in the alkyl- and aryl-cuprate intermediates, which precedes the
CC bond formation, and determines the configuration of the product. The copper
enolate intermediates can also be trapped by TMS triflate or triflic anhydride giving
directly the versatile chiral enolsilanes or enoltriflates that can be used in further
transformations (Scheme2.30) [110].
O
ZnR'2 or R'MgX, Cu(OTf)2

O
NHC or Ag(NHC)X
ZnR'2 , Cu(OTf)2, TMSOTf or Tf2O
NHC or Ag(NHC)X
R'
R TMS(OTf)
O
R'
R
Scheme2.30 Copper-catalysed asymmetric conjugate addition of organozincs to enones
Similarly, highly enantioselective transformations were reported by using other

chiral functionalised non-symmetric (138) or C2 symmetric NHC pro-ligands (139
140) (Fig.2.24) in the presence of organometallic bases and copper salts [111, 112].
t Bu
+ N
Mes N
PF6
138
Ph
Ph
Ph
N + N
N + N
HO
139
Ph
PF6
OMe MeO
140
BF4
Fig.2.24 Chiral NHC pro-ligands used in copper-catalysed asymmetric conjugate additions
The asymmetric 1,4-conjugate addition of phenyl boronic acids to cyclohex-2-enone

was catalysed by the Pd complex 141 (Fig.2.25). Good to excellent yields and high ee
(9097%) were obtained under mild conditions and low catalyst loadings (rt, 3 mol%)
56
A. A. Danopoulos
in THF/H2O in the presence of base (KOH or K2CO3). The labile acetates in 141 are
crucial for the success of the reaction as demonstrated by the inactivity of the corresponding iodide complexes. Interestingly, the configuration of the isolated addition product is
the opposite to that obtained by the analogous Rh-(binap) catalysed reaction with ligand
of the same configuration [113]. Other cyclic enones gave similar results. A plausible
catalytic cycle involves reaction of the catalyst with base to form the corresponding
hydroxo palladium complex which undergoes transmetallation with the phenyl boronic
acids. Insertion of the C=C bond of the enone into the PdC bond gives the oxa-allyl
species 142 or the enolate 143 which are releasing the product after hydrolysis.
Pd
N
O
X
Pd
Pd
O
142
143
141
X=OOCCH3, OOCCF3, I
Fig.2.25 Palladium catalysts and postulated intermediates in the asymmetric conjugate addition
of phenyl boronic acids to cyclohex-2-enone
The enantioselective b-borylation of a,b-unsaturated esters with (Bpin)2 was

studied in the presence of various [CuCl(NHC)] or [Cu(MeCN)(NHC)]+ (NHC =
chiral imidazol-2-ylidene or imidazolidin-2-ylidene) complexes. The reaction proceeds by heterolytic cleavage of the BB bond of the (Bpin)2, followed by formation of Cu-boryl complexes which insert across the C=C bond of the unsaturated
ester. Best yields and ee were observed with complex 144, featuring a non-C2
symmetric NHC ligand (Scheme2.31) [114].
Ph
O
144
OEt (Bpin)2, NaOt Bu, MeOH
Bpin O
Ph
N
OEt
N
Cu
Cl
144
Scheme2.31 Copper-catalysed asymmetric borylation of conjugated enones
Further insight into the b-borylation reaction of a,b-enones (Scheme2.32) showed

that the reaction can be carried out in THF, and the catalyst generated in situ from CuCl
(5 mol%), the imidazolium salt (5 mol%), and NaOtBu (10 mol%), to form the [Cu(OtBu)
(NHC)] as the catalysis initiating species. In this case, stable boron enolate products are
formed which need to be hydrolysed by methanol to the ketone products [114].
57
[Cu(NHC)] +
Cu(NHC)
O
(Bpin)2
B(pin)
O
(Bpin)2
B(pin)
(NHC)Cu(B(pin)
B(pin)
Scheme2.32 Borylation of enone mediated by Cu-NHC complexes
2.12Chloroesterification and Chloroacetylation Reactions

The rare chloroesterification of terminal alkynes (i.e. the addition of ClCOOR
across the CC triple bond) catalysed by [RhCl(CO)(PPh3)2] gave Z-b-choro-a,bunsaturated esters (Scheme2.33) [115].
+ ClCOOR'
[RhCl(CO)(PPh3)2] 1 mol%
toluene,
100oC
Cl
R
COOR'
R'OOC
R
major
Cl
minor
Scheme2.33 Products in the rhodium catalysed-chroroesterification of alkynes
The chloroesterification of terminal alkynes or conjugated enynes by ClCOOMe

was catalysed by complex [RhCl(IPr)(1,5-cod)] (1 mol%) under similar conditions
as the [RhCl(CO)(PPh3)2]. High conversions (7080%) were obtained with high
regio- and stereo-selectivity. Here too, Markovnikov, Z-additions products were
dominant. Under similar conditions the complex [RhCl(1,5-cod)(PPh3)] gave lower
conversions (ca. 20%) [116].
Chloroacylation of terminal aryl, alkyl or alkenyl alkynes [i.e. the addition of
RC(=O)Cl across the CC triple bond] with aromatic acyl chlorides was catalysed
by [IrCl(cod)(IPr)] (5 mol%) in good conversions (7094%) in toluene (90C, 20
h). Z-addition products were observed only. Internal alkynes were unreactive.
Surprisingly, a phosphine/[Ir(m-Cl)(1,5-cod)]2 system under the same conditions
provides decarbonylation products (Scheme2.34) [117].
R'
[Ir(-Cl)(1,5-cod)]2
Cl
OiPr
R'
R
Cl
,CO
P OiPr
Cy2
R
O
R'
Cl
[IrCl(1,5-cod)(IPr)]
R'
Cl
R
Scheme2.34 Chloroacylation of alkynes catalysed by iridium NHC complexes
58
A. A. Danopoulos
2.13Conclusion
Since the isolation of relatively stable nucleophilic carbenes, their use as ligands for
almost all metals of the Periodic Table and their applications in homogeneous
catalysis have risen exponentially. This is attested by the increasing number of
researchers from diverse backgrounds that are entering this area of study. The
deeper understanding of the steric and electronic characteristics of the carbene
ligands, and the way they interact with the metal in a catalytic species promise new
developments in the rational design of more active, selective and stable catalysts
for numerous applications [118]. We believe that exciting developments in this area
will appear in the near future.
References

1. Praetorius JM, Wang R, Crudden CM (2009) Eur J Inorg Chem 13:17461751

2. Yu X-Y, Sun H, Brian PO, James BR (2009) Eur J Inorg Chem 13:17521758
3. Huang J, Stevens ED, Nolan SP (2000) Organometallics 19:11941197
4. Hillier AC, Lee HM, Stevens ED, Nolan SP (2001) Organometallics 20:42464252
5. Herrmann WA, Frey GD, Herdtweck E, Steinbeck M (2007) Adv Synth Catal 349:16771691
6. Allen DP, Crudden CM, Calhoun LA, Wang R, Decken A (2005) J Organomet Chem
690:57365746
7. Baskakov D, Herrmann WA, Herdtweck E, Hoffmann SD (2007) Organometallics
26:626632
8. Herrmann WA, Baskakov D, Herdtweck E, Hoffmann SD, Bunlaksananusorn T, Rampf F,
Rodefeld L (2006) Organometallics 25:24492456
9. Lee HM, Smith DC Jr, He Z, Stevens ED, Yi CS, Nolan SP (2001) Organometallics
20:794797
10. Dinger MB, Mol JC (2003) Eur J Inorg Chem 28272833
11. Dharmasena UL, Foucault HM, dos Santos EN, Fogg DE, Nolan SP (2005) Organometallics
24:10561058
12. Grasa GA, Moore Z, Martin KL, Stevens ED, Nolan SP, Paquet V, Lebel HJ (2002)
JOrganomet Chem 658:126131
13. Jazzar RFR, Macgregor SA, Mahon MF, Richards SP, Whittlesey MK (2002) J Am Chem
Soc 124:49444945
14. Edwards MG, Jazzar RFR, Paine BM, Shermer DJ, Whittlesey MK, Williams JMJ, Edney
DD (2004) Chem Commun 9091
15. Chantler VL, Chatwin SL, Jazzar RFR, Mahon MF, Saker O, Whittlesey MK (2008) Dalton
Trans 26032614
16. Vazquez-Serrano LD, Owens BT, Buriak JM (2002) Chem Commun 25182519
17. Sprengers JW, Wassenaar J, Clement ND, Cavell KJ, Elsevier CJ (2005) Angew Chem Int
Ed 44:20262029
18. Jurcik V, Nolan SP, Cazin CSJ (2009) Chem Eur J 15:25092511
19. Heckenroth M, Kluser E, Neels A, Albrecht M (2007) Angew Chem Int Ed 46:62936296
20. Nanchen S, Pfaltz A (2006) Chem Eur J 12:45504558
21. Powell MT, Hou DR, Perry MC, Cui X, Burgess K (2001) J Am Chem Soc 123:
88788879
22. Gunther, H (2004) Synlett 17891793
59
23. Perry MC, Cui X, Powell MT, Hou DR, Reibenspies JH, Burgess K (2003) J Am Chem Soc
125:113123
24. Fan Y, Cui X, Burgess K, Hall B (2004) J Am Chem Soc 126:1668816689
25. Corma A, Puebla-Gutierrez E, Iglesias M, Monge A, Perez-Ferreras S, Sanchez F (2006)
Adv Synth Catal 348:18991907
26. Hillier AC, Lee HM, Stevens ED, Nolan SP (2001) Organometallics 20:42464252
27. Gnanamgari D, Moores A, Rajaseelan E, Crabtree RH (2007) Organometallics 26:
12261230
28. Gnanamgari D, Sauer ELO, Schley ND, Butler C, Incarvito CD, Crabtree RH (2009)
Organometallics 28:321325
29. Danopoulos AA, Winston S, Motherwell WB (2002) Chem Commun 13761377
30. Peris E, Mata JA, Crabtree RH, Poyatos M (2003) Organometallics 22:11101114
31. Crabtree RH, Faller JW (2002) Organometallics 21:35963604
32. Peris E, Mas-Marza E, Sanau M (2005) Inorg Chem 44:99619967
33. Stylianides N, Danopoulos AA, Tsoureas N (2005) J Organomet Chem 690:59485958
34. Wang CY, Fu CF, Liu YH, Peng SM, Liu ST (2007) Inorg Chem 46:57795786
35. Turkmen H, Pape T, Hahn FE, Cetinkaya B (2008) Eur J Inorg Chem 54185423
36. Yang L, Kruger A, Neels A, Albrecht M (2008) Organometallics 27:31613171
37. Danopoulos AA, Fiddy SG, Evans J, Neisius T, Newton MA, Tsoureas N, Tulloch AAD
(2007) Chem Eur J 13:36523659
38. Miecznikowski JR, Crabtree RH (2004) Organometallics 23:629631
39. Kuhl S, Schneider R, Fort Y (2003) Organometallics 22:41844186
40. Peris E, da Costa AP, Viciano M, Sanau M, Merino S, Tejeda J, Royo B (2008)
41. Guillena G, Ramon DJ, Yus M (2007) Angew Chem Int Ed 46:23582364
42. Crabtree RH, Faller JW (2002) Organometallics 21:35963604
43. Castarlenas R, Esteruelas MA, Onate E (2008) Organometallics 27:32403247
44. Berthon-Gelloz G, Buisine O, Briere JF, Michaud G, Sterin S, Mignani G, Tinant B,
Declercq JP, Chapon D, Marko IE (2005) J Organomet Chem 690:61566168
45. Sprengers JW, Mars MJ, Duin MA, Cavell KJ, Elsevier CJ (2003) J Organomet Chem
679:149152
46. De Bo G, Berthon-Gelloz G, Tinant B, Marko IE (2006) Organometallics 25:18811890
47. Poyatos M, Mas-Marza E, Mata JA, Sanau M, Peris E (2003) Eur J Inorg Chem
12151221
48. Mas-Marza E, Sanau M, Peris E (2005) Inorg Chem 44:99619967
49. Jimenez MV, Perez-Torrente JJ, Bartolome MI, Gierz V, Lahoz FJ, Oro LA (2008)
50. Chaulagain MR, Mahandru GM, Montgomery J (2006) Tetrahedron 62:75607566
51. Dez-Gonzlez S, Nolan SP (2008) Acc Chem Res 41:349358
52. Dez-Gonzlez S, Scott NM, Nolan SP (2006) Organometallics 25:23552358
53. Kaur H, Zinn FK, Stevens ED, Nolan SP (2004) Organometallics 23:11571160
54. Dez-Gonzlez S, Stevens ED, Scott NM, Petersen JL, Nolan SP (2008) Chem Eur J
14:158168
55. Faller JW, Fontaine P (2006) Organometallics 25:58875893
56. Cesar V, Bellemin-Laponnaz S, Wadepohl H, Gade LH (2005) Chem Eur J 11:28622873
57. Schneider N, Kruck M, Bellemin-Laponnaz S, Wadepohl H, Gade LH (2009) Eur J Inorg
Chem 493500
58. Thomas RL, Souza FES, Marder TB (2001) J Chem Soc Dalton Trans 16501656
59. Mann G, John KD, Baker RT (2000) Org Lett 2:21052108
60. Baker RT, Nguyen P, Marder TB, Westcott SA (1995) Angew Chem Int Ed 34:13361338
61. Dai C, Robins EG, Scott AJ, Clegg W, Yufit DS, Howard JAK, Marder TB (1998) Chem
Commun 19831984
62. Ramirez J, Corberan R, Sanau M, Peris E, Fernandez E (2005) Chem Commun 30563058
60
A. A. Danopoulos
63. Corberan R, Ramirez J, Poyatos M, Peris E, Fernandez E (2006) Tetrahedron Asymm

17:17591762
64. Lillo V, Mata J, Ramirez J, Peris E, Fernandez E (2006) Organometallics 25:58295831
65. Lillo V, Mas-Marza E, Segarra AM, Carbo JJ, Bo C, Peris E, Fernandez E (2007) Chem
Commun 33803382
66. Peris E, Corberan R, Lillo V, Mata J, Fernandez E (2007) Organometallics 26:43504353
67. Laitar DS, Tsui EY, Sadighi JP (2006) Organometallics 25:24052408
68. Lillo V, Fructos MR, Ramirez JB, Maseras F, Diaz-Requejo MM, Perez PJ, Fernandez E
(2007) Chem Eur J 13:26142621
69. Lillo V, Mata JA, Segarra AM, Peris E, Fernandez E (2007) Chem Commun 21842186
70. Khramov DM, Rosen EL, Vu PD, Lynch VM, Bielawski CW (2008) Tetrahedron
64:68536862
71. Lee Y, Hoveyda AH (2009) J Am Chem Soc 131:31603161
72. Beller M, Seayad J, Tillack A, Jiao H (2004) Angew Chem Int Ed 43:33683398
73. Muller TE, Yus M, Mizuki T (2008) Chem Rev 108:37953892
74. Takaki K, Koizumi S, Yamamoto Y, Komeyama K (2007) Tetrahedron Lett 48:46434644
75. Field LD, Messerle BA, Vuong KQ, Turner P (2005) Organometallics 24:42414250
76. Burling S, Field LD, Li HL, Messerle BA, Turner P (2003) Eur J Inorg Chem 31793184
77. Bauer EB, Andavan GTS, Hollis TK, Rubio RJ, Cho J, Kuchenbeiser GR, Helgert TR, Letko
CS, Tham FS (2008) Org Lett 10:11751178
78. Cho J, Hollis TK, Helgert TR, Valente EJ (2008) Chem Commun 50015003
79. Gischig S, Togni A (2005) Eur J Inorg Chem 47454754
80. Houghton J, Dyson G, Douthwaite RE, Whitwood AC, Kariuki BM (2007) Dalton Trans
30653073
81. Munro-Leighton C, Delp SA, Blue ED, Gunnoe TB (2007) Organometallics 26:14831493
82. Munro-Leighton C, Delp SA, Alsop NM, Blue ED, Gunnoe TB (2008) Chem Commun
111113
83. Kinder RE, Zhang Z, Widenhoefer RA (2008) Org Lett 10:31573159
84. Malyshev DA, Scott NM, Marion N, Stevens ED, Ananikov VP, Beletskaya IP, Nolan SP
(2006) Organometallics 25:44624470
85. Delp SA, Munro-Leighton C, Goj LA, Ramirez MA, Gunnoe TB, Petersen JL, Boyle PD
(2007) Inorg Chem 46:23652367
86. Zhang Z, Widenhoefer RA (2008) Org Lett 10:20792081
87. Marion N, Ramon RS, Nolan SP (2009) J Am Chem Soc 13:448449
88. De Fremont P, Singh R, Stevens ED, Petersen JL, Nolan SP (2007) Organometallics
26:13761385
89. Zhang Z, Du Lee S, Fisher AS, Widenhoefer RA (2009) Tetrahedron 65:17941798
90. Viciu MS, Stevens ED, Petersen JL, Nolan SP (2004) Organometallics 23:37523755
91. Biffis A, Tubaro C, Buscemi G, Basato M (2008) Adv Synth Catal 350:189196
92. Marion N, Diez-Gonzalez S, de Fremont P, Noble AR, Nolan SP (2006) Angew Chem Int Ed
45:36473650
93. Sato Y, Yoshin T, Mori M (2003) Org Lett 3133
94. Sato Y, Yoshino T, Mori M (2005) J Organomet Chem 690:57535758
95. Visentin F, Togni A (2007) Organometallics 26:37463754
96. Rosenblade SJ, Ros A, Monge D, Alcarazo M, Alvarez E, Lassaletta JM, Fernandez R (2007)
97. Bonnet LG, Douthwaite RE, Kariuki BM (2003) Organometallics 22:41874189
98. Toselli N, Martin D, Buono G (2008) Org Lett 10:14531456
99. Lee K, Brown MK, Hird AW, Hoveyda AH (2006) J Am Chem Soc 128:71827184
100. Van Veldhuizen JJ, Campbell JE, Giudici RE, Hoveyda AH (2005) J Am Chem Soc
127:68776882
101. Lee Y, Akiyama K, Gillingham DG, Brown MK, Hoveyda AH (2008) J Am Chem Soc
130:446447
61
102. Yasar S, Ozdemir I, Cetinkaya B, Renaud JL, Bruneau C (2008) Eur J Org Chem
21422149
103. Plietker B, Dieskau A, Moews K, Jatsch A (2008) Angew Chem Int Ed 47:198201
104. Barczak NT, Grote RE, Jarvo ER (2007) Organometallics 26:48634865
105. Fraser PK, Woodward S (2001) Tetrahedron Lett 42:27472749
106. Winn CL, Guillen F, Pytkowicz J, Roland S, Mangeney P, Alexakis A (2005) J Organomet
Chem 690:56725695
107. Arnold PL, Rodden M, Davis KM, Scarisbrick AG, Blake AJ, Wilson C (2004) Chem
Commun 16121613
108. Clavier H, Coutable L, Toupet L, Guillemin J-C, Mauduit M (2005) J Organomet Chem
690:52375254
109. Lee K, Hoveyda AH (2009) J Org Chem 74:44554462
110. Lee K, Brown MK, Hird AW, Hoveyda AH (2006) J Am Chem Soc 128:71837184
111. Martin D, Kehrli S, dAugustin M, Clavier H, Mauduit M, Alexakis A (2006) J Am Chem
Soc 128:84168417
112. Matsumoto Y, Yamada K, Tomioka K (2008) J Org Chem 73:45784581
113. Zhang T, Shi M (2008) Chem Eur J 14:37593764
114. Lillo V, Prieto A, Bonet A, Diaz-Requejo MM, Ramirez J, Perez PJ, Fernandez E (2009)
115. Hua R, Shimada S, Tanaka M (1998) J Am Chem Soc 120:1236512366
116. Sim H, Baek JY (2008) Synlett 551554
117. Iwai T, Fujihara T, Terao J, Tsuji Y (2009) J Am Chem Soc 131:66686669
118. For a recent review on Late Transition Metal-NHC complexes and catalysis see: DezGonzlez S, Marion N, Nolan SP (2009) Chem Rev 109:36123676
http://www.springer.com/978-90-481-2865-5

c2 PDF

Uploaded by

Document Informationclick to expand document information

Document Informationclick to expand document information

Copyright:

Available Formats

c2 PDF

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

c2 PDF

Uploaded by

Copyright:

Available Formats

Chapter 2

N-Heterocyclic Carbene Complexes

Abstract The use of N-heterocyclic carbene (NHC) complexes as homogeneous

2.2Hydrogenation of Alkenes and Alkynes

Scheme2.1 Reactions of Rh(I) NHC complexes with hydrogen

The hydrogenation activity of the isolated hydrides 3 and 6 towards cyclooctene

2 N-Heterocyclic Carbene Complexes in Additions to Multiple Bonds

P(OPh)3) and trans-[RhCl(ICy)2PPh3] showed poor activity compared to Crabtrees

Replacement of one PCy3 in [RuCl(H)(CO)(PCy3)2] 10 by IMes gave [RuCl(H)

Fig.2.2 Ruthenium-based hydrogenation catalysts bearing NHC ligands

Reduction of acetophenone by iPrOH/H2 has been studied with the ruthenium

2 N-Heterocyclic Carbene Complexes in Additions to Multiple Bonds

Recently, the direct hydrogenation of a wide range of alkenes was successfully

The development of functionalised NHC ligands, bearing NHC functional

coordinated alkene. The face selectivity is determined by the interaction of the

Fig.2.6 Chiral functionalised NHC complexes as enantioselective hydrogenation catalysts with

The supported Au complexes presented in Scheme2.3 show increased activity in the

support = silica, MCM-41, ITQ2

Scheme2.3 Hydrogenations catalysed by a supported Au-NHC complex

2.3Transfer Hydrogenation and Related Reactions

2 N-Heterocyclic Carbene Complexes in Additions to Multiple Bonds

2 N-Heterocyclic Carbene Complexes in Additions to Multiple Bonds

Scheme2.5 Products formed in the transfer hydrogenation reduction of nitroarenes by complex 35

This behaviour was rationalised by a stepwise reduction mechanism, in which a

Therefore, improved chemo- and stereo-selectivities of the catalysts are

Scheme2.7 Platinum-NHC complexes as hydrosilylation catalysts

Complexes of the type 4853 (Scheme2.7) have been targeted as pre-catalysts

2 N-Heterocyclic Carbene Complexes in Additions to Multiple Bonds

only the anti-Markovnikov addition product is observed. The complexes 5052

Fig.2.9 Hydrosilylation catalysts based on Rh- and Ir-NHC complexes

Complexes 59 and 60 catalyse the hydrosilylation of phenylacetylene (but not

2 N-Heterocyclic Carbene Complexes in Additions to Multiple Bonds

Scheme2.8 Rationalisation of the selectivity observed in the hydrosilylation of alkynes by the

Scheme2.9 Hydrosilylation of carbonyl compounds to silyl ethers

The hydrosilylation of carbonyl compounds by Et3SiH catalysed by the copper

2 N-Heterocyclic Carbene Complexes in Additions to Multiple Bonds

Fig.2.10 Hydrosilylation catalysts of carbonyl compounds based on Cu-NHC complexes

Scheme2.10 Intermediates in the Cu-catalysed hydrosilylation of carbonyl compounds

The Rh-catalysed asymmetric hydrosilylation of prochiral ketones has been

2.5Hydroboration and Diboration Reactions

2 N-Heterocyclic Carbene Complexes in Additions to Multiple Bonds

The Ag complex 74 catalyses the diboration of internal and terminal alkenes to

Fig.2.13 Diboration catalysts based on palladium and iridium NHC complexes

The Ir complexes 83 or [Ir(IMes)Cl2Cp*], in the presence of NaOAc and excess

2 N-Heterocyclic Carbene Complexes in Additions to Multiple Bonds

Scheme2.11 Hydroboration of arylalkenes catalysed by copper NHC complexes

Scheme2.12 Enantioselective hydroboration of arylalkenes catalysed by copper NHC complexes

The pincer complexes 8990 (Fig.2.14) catalyse the intramolecular hydroamination/

2 N-Heterocyclic Carbene Complexes in Additions to Multiple Bonds

Fig.2.15 Hydroamination catalysts based on palladium NHC complexes

Scheme2.13 Intermolecular hydroamination of activated alkenes

Fig. 2.16 Copper-amido complexes as catalysts for the intermolecular hydroamination of

by the electron-withdrawing groups NO2 CN, CF3 but not Cl, Br or H

X = NO2, CN, CF3

Scheme2.14 Copper-catalysed intermolecular hydroamination of electron-deficient aryl alkenes

The hydroaminations of electron-deficient alkenes with aniline or small primary

Scheme2.15 Postulated mechanism for the copper-catalysed hydroamination of electron-deficient

2.2Hydrogenation of Alkenes and Alkynes

2.3Transfer Hydrogenation and Related Reactions

2.5Hydroboration and Diboration Reactions

2.10Allylic Alkylations and Other Substitution Reactions

2.11Additions to Conjugated Enones and Related Reactions

2.12Chloroesterification and Chloroacetylation Reactions