CN113000066B - A kind of Z-selective ruthenium carbene olefin metathesis catalyst and its preparation method and application - Google Patents

Abstract

The invention discloses a Z-selective ruthenium carbene olefin metathesis catalyst, which utilizes the strong electron drawing characteristic of bromine atoms to improve the reaction activity of the catalyst; the addition of bromine atoms also increases the steric hindrance of the whole ligand, and improves the selectivity of the catalyst; the complex has a triangular bipyramidal coordination structure close to a middle transition state under the action of large steric hindrance, and the catalytic activity of the catalyst is improved. The catalyst also improves the stability and temperature resistance of the catalyst by inhibiting the nucleophilic addition reaction of sulfur atoms to benzylidene carbene carbon. The invention also discloses a preparation method of the catalyst, the method has simple steps and mild reaction conditions, and the obtained catalyst has excellent thermal stability. The invention also discloses application of the catalyst in catalyzing ruthenium carbene olefin metathesis reaction to prepare Z-type olefin products, and the catalyst can be used for catalyzing olefin reaction to obtain cis-products with specific configurations, and has the characteristics of high catalytic activity, high selectivity and high product yield.

Description

A kind of Z-selective ruthenium carbene olefin metathesis catalyst and its preparation method and application

technical field

The invention belongs to the field of transition metal organic catalysts, and relates to a Z-selective ruthenium carbene olefin metathesis catalyst and a preparation method and application thereof.

Background technique

Olefins with Z-structure have a wide range of applications in the fields of chemistry, biology and medicine, and they need to be prepared by fast, efficient and stereoselective catalytic reactions, and the key to catalytic reactions is catalysts. Many natural open-chain compounds (such as oleic acid, linolenic acid), natural macrocyclic compounds (such as civet ketone, etc.), and some substances with anticancer activity all contain Z-alkene structures, but traditional alkenes contain Z-alkene structures. Metathesis catalysts often obtain a high proportion of E-type olefins in catalyzing the cross-metathesis reaction (CM) of open-chain olefins and the metathesis reaction (RCM) of ring-closed olefins forming macrocycles. Therefore, how to reshape the catalyst structure to obtain Z-form olefin structure products with high selectivity in the catalytic process has become a hot spot in the field of olefin metathesis research.

The research in the field of olefin metathesis has achieved breakthrough research results, but still faces huge difficulties and challenges. In 2011, Grubbs' research group reported a carboxyl-chelated Z-selective ruthenium carbene olefin metathesis catalyst for the first time, realizing the Z-type catalysis of cross metathesis for the first time. However, such catalysts are unstable, have low catalytic activity and are easily decomposed. Subsequent studies found that the catalytic activity and Z-selectivity of the catalyst were greatly improved after replacing the carboxyl group in the catalyst with a nitro group, but the problem of easy decomposition of this type of catalyst remained unsolved. In 2013, Hoveyda's group found that when 1,2-benzenedithiophenol is used as a ligand to replace two chlorine atoms in a compound, the formed complex can catalyze the ring-opening cross-metathesis reaction of the strained ring, and obtain a certain Z proportional product. The inventors found in 2019 that the catalyst showed excellent stability when 3,4-dimercapto-1-cyclobutene-1,2-dione was used to replace 2,5-dichlorobenzenedimercapto, even in air. can also be stored for a long time. The 1,8-naphthalene dimercapto-chelated catalysts found in our subsequent study have very high Z-selectivity but low catalytic activity.

As can be seen from the above, the prior art has the following deficiencies: although some achievements have been made in the research on Z-selective olefin metathesis catalysts, it is still found that there are general rules to follow; this type of catalyst is few, and the reported catalysts The selectivity and activity need to be further improved. Nitro-chelated six-coordination Grubbs-type catalysts have high catalytic activity and selectivity, but the synthesis process is complex, the stability is poor, and the functional group applicability is not high. The newly emerging ruthenium carbene catalysts containing disulfide chelate ligands have a simple synthesis process, good functional group applicability, and great application prospects. However, the activity and Z-selectivity of ruthenium carbene catalysts based on disulfide chelate ligands still need to be further optimized.

SUMMARY OF THE INVENTION

In order to overcome the deficiencies of the prior art, one of the objects of the present invention is to provide a Z-selective ruthenium carbene olefin metathesis catalyst, which has higher Z-form selectivity and stability in the catalytic ruthenium carbene olefin metathesis reaction Better and higher catalytic efficiency.

The second purpose of the present invention is to provide a preparation method of a Z-selective ruthenium carbene olefin metathesis catalyst.

The third object of the present invention is to provide the application of Z-selective ruthenium carbene olefin metathesis catalyst in catalyzing ruthenium carbene olefin metathesis reaction to prepare Z-form olefin product.

One of the objects of the present invention is to adopt the following technical scheme to realize:

A Z-selective ruthenium carbene olefin metathesis catalyst has the general structural formula I:

wherein Mes is 2,4,6-trimethylphenyl.

The second purpose of the present invention adopts the following technical scheme to realize:

The preparation method of above-mentioned Z-selective ruthenium carbene olefin metathesis catalyst, comprises the following steps:

in:

Under nitrogen, combine Hoveyda catalyst (A) with 2,4,5,7-tetrabromo-1,8-dimercaptozinc salt (B) or 2,4,5,7-tetrabromo-1,8-bis Sodium thiosulfate (C) is dissolved in an organic solvent, dried under vacuum after stirring, centrifuged after adding dichloromethane, and the solvent is removed to obtain the final product I, namely 2,4,5,7-tetrabromo-1,8-naphthalene Dithioruthenium carbene compound.

Further, the organic solvent is tetrahydrofuran.

Further, the stirring temperature was 0°C and the time was 0.5h.

Preferably, the synthetic steps of compound B and compound C are:

Reference for the synthesis of compounds 1-4: R.J.Wright, C.Lim, T.D.Tilley, Chem.Eur.J. 2009, 15, 8518.

Under nitrogen protection, compound 3 (505.6 mg, 1 mmol) was dissolved in 20 mL of tetrahydrofuran, and LiAlH ₄ (114.0 mg, 3 mmol) was slowly added at 0° C. to react for 1 h. After the reaction, 1M HCl (10 mL) was added, extracted with chloroform, dried over anhydrous sodium sulfate, and the solvent was removed to obtain compound 4 (219.3 mg, 0.43 mmol).

Compound 4 (507.6 mg, 1 mmol), Zn(OAc) ₂ ·2H ₂ O (876.9 mg, 4 mmol, 4.0 equiv.), ethylenediamine (0.40 mL, 6 mmol, 6.00 equiv.) were placed in a 25 mL round bottom flask, 10 mL of isopropanol was added, and the mixture was stirred at room temperature for 2 h. The solid precipitate was obtained by filtration, which was washed with methanol (3 times with 5 mL) and chloroform (3 times with 5 mL), respectively. After draining, compound B (415.8 mg, 0.73 mmol) was obtained as a yellow solid.

Compound 4 (507.6 mg, 1 mmol) and sodium tert-butoxide (107.9 mg, 1.1 equiv.) were dissolved in 10 mL of methanol, stirred for 20 min, spin-dried, washed with petroleum ether to obtain yellow compound C (518.5 mg, 0.94 mmol) .

The third purpose of the present invention adopts the following technical scheme to realize:

The application of the above-mentioned Z-selective ruthenium carbene olefin metathesis catalyst in catalyzing ruthenium carbene olefin metathesis reaction to prepare Z-form olefin product.

Compared with the prior art, the beneficial effects of the present invention are:

1. The present invention provides a Z-selective ruthenium carbene olefin metathesis catalyst, which utilizes the strong electron-pulling characteristics of bromine atoms in 2,4,5,7-tetrabromo-1,8-naphthalene dithiol to reduce metal ruthenium The electron cloud density in the center makes it easier to coordinate with the alkene, which increases the rate of the transition state of the metal quaternary ring, thereby improving the reactivity of the catalyst.

The catalyst provided by the invention improves the stability and temperature resistance of the complex by inhibiting the nucleophilic addition reaction of the sulfur atom to the benzylidene carbene carbon; at the same time, the addition of the bromine atom can increase the steric hindrance of the whole ligand, and further Improve catalyst selectivity.

The present invention utilizes the large steric hindrance effect of 2,4,5,7-tetrabromo-1,8-naphthalene dithiol ligand to increase the repulsive force between it and azacyclic carbene ligand, thereby forcing the ligand As far as possible, the complex is far away from the nitrogen heterocyclic carbene ligand, which also has a large steric hindrance, so that the complex has a trigonal bipyramid coordination structure close to the intermediate transition state, which improves the catalytic activity of the catalyst; the large steric hindrance of the ligand will also make The transition state generated by the complex during the reaction has a more compact steric environment, thereby improving the steric control ability of the substituent group in the transition state of the four-membered ring.

2. The present invention also provides a preparation method of the catalyst. The method has simple steps, mild reaction conditions, and the prepared product has excellent thermal stability.

3. The present invention also provides the application of this catalyst in catalyzing ruthenium carbene olefin metathesis reaction to prepare Z-form olefin product, this catalyst catalyzing olefin reaction can obtain the cis product of specific configuration, has high catalytic activity, Z-form selectivity high product yield.

Description of drawings

FIG. 1 is a graph showing the results of the thermal stability test of the catalyst of the present invention.

Detailed ways

The present invention will be further described below with reference to the specific embodiments and the accompanying drawings. It should be noted that, under the premise of no conflict, the embodiments or technical features described below can be arbitrarily combined to form new embodiments.

Example 1

A Z-selective ruthenium carbene olefin metathesis catalyst has the general structural formula I, and the preparation process is as follows: under the protection of nitrogen, in a 10 mL round-bottomed flask, mix Hoveyda catalyst A (187.5 mg, 2.4 mmol) with 2, 4, 5 ,7-Tetrabromo-1,8-dimercaptozinc salt B (236.0 mg, 0.4 mmol) was dissolved in 5 mL of tetrahydrofuran, stirred at 0 °C for 0.5 h, vacuum-dried after the reaction, added with dichloromethane and centrifuged to remove After solvent, a brownish yellow solid powder was obtained, that is, the final product I (196.4 mg, yield 74.1%).

¹ H NMR (400 MHz, CDCl ₃ ) δ 15.38 (s, 1H), 7.32 (d, J=13.6 Hz, 2H), 7.04-6.91 (m, 3H), 6.85-6.67 (m, 3H), 3.99 ( d, J=7.6Hz, 3H), 2.61–2.39 (m, 9H), 2.21 (t, J=26.3Hz, 9H), 1.80 (d, J=6.7Hz, 4H), 1.51 (d, J=6.6 Hz,3H). ¹³ C NMR(101MHz,CDCl ₃ )δ153.99,142.31,141.42,140.93,135.26,132.32,131.32,131.18,129.50,129.22,127.34,126.40,124.29,124.01,122.69,122.01,115.59,80.77, 53.63, 51.43, 24.33, 21.58, 21.18, 19.23 ppm. ESI-MS[M]+calcd for C ₄₁ H ₄₁ Br ₄ N ₂ ORuS ₂ : 1061.8318; found: 1061.8346.

Example 2

The difference between Example 2 and Example 1 is: replace 2,4,5,7-tetrabromo-1,8 with sodium 2,4,5,7-tetrabromo-1,8-bisthioate (C) -Dithiolzinc salt (B), the rest are the same as in Example 1 to obtain the final product I (145.6 mg, yield 54.9%).

¹ H NMR (400 MHz, CDCl ₃ ) δ 15.38 (s, 1H), 7.32 (d, J=13.6 Hz, 2H), 7.04-6.91 (m, 3H), 6.85-6.67 (m, 3H), 3.99 ( d, J=7.6Hz, 3H), 2.61–2.39 (m, 9H), 2.21 (t, J=26.3Hz, 9H), 1.80 (d, J=6.7Hz, 4H), 1.51 (d, J=6.6 Hz,3H).13C NMR(101MHz,CDCl3)δ153.99,142.31,141.42,140.93,135.26,132.32,131.32,131.18,129.50,129.22,127.34,126.40,124.29,124.01,122.69,122.01,115.59,80.77,53.63, 51.43, 24.33, 21.58, 21.18, 19.23ppm.

Experimental example 1

Catalytic generation: ((Z)-2-((1'S,3'R)-3'-vinylcyclopentyl)vinyl)benzene

Under nitrogen protection, 14.3 mg (0.15 mmol) of norbornene and 312.3 mg (3 mmol) of styrene were added to the reaction test tube, and then 1 mL of THF dissolved with 4.8 mg (4.5 μmol, 3.0 mol%) of the catalyst obtained in Example 1 was added. (tetrahydrofuran) solution, stirred at room temperature for 4h. After the reaction, the product was passed through a silica gel column (10% ethyl acetate in petroleum ether solution-60% ethyl acetate in petroleum ether solution) to finally obtain 28.1 mg of colorless oil (yield 95.0%), Z/E was 98: 2.

¹ H NMR (600 MHz, CDCl ₃ ): δ 7.36-7.31 (m, 2H), 7.28-7.21 (m, 3H), 6.37 (d, J=11.5 Hz, 1H), 5.83 (ddd, J=17.4, 10.2, 7.4Hz, 1H), 5.59 (dd, J=11.5, 10.0Hz, 1H), 5.00 (ddd, J=17.1, 2.0, 1.2Hz, 1H), 4.91 (ddd, J=10.2, 1.9, 1.0Hz) ,1H),3.20–2.90(m,1H),2.67–2.43(m,1H),2.15–2.00(m,1H),1.97–1.80(m,2H),1.63–1.46(m,2H),1.24 (dt, J=12.5, 10.4Hz, 1H). ¹³ C NMR (151MHz, CDCl3) δ 143.15, 138.05, 137.92, 128.71, 128.24, 127.72, 126.59, 112.66, 44.65, 41.55, 38.79, 33.13, 32.04ppm.

Experimental example 2

Catalytic production: (Z)-1-fluoro-4-(2-((1'S,3'R)3'-vinylcyclopentyl)vinyl)benzene

Under nitrogen protection, 14.3 mg (0.15 mmol) of norbornene and 366.2 mg (3 mmol) of 4-fluorostyrene were added to the reaction test tube, and then 4.8 mg (4.5 μmol, 3.0 mol%) of the catalyst obtained in Example 1 was added. 1 mL of THF (tetrahydrofuran) solution, stirred at room temperature for 4 h. After the reaction, the product was passed through a silica gel column (10% ethyl acetate in petroleum ether solution-60% ethyl acetate in petroleum ether solution) to finally obtain 30.2 mg of colorless oil (yield 93.0%), Z/E was 99: 1.

¹ H NMR (600 MHz, CDCl ₃ ) δ 7.22-7.18 (m, 2H), 7.03-6.96 (m, 2H), 6.31 (d, J=11.5 Hz, 1H), 5.82 (ddd, J=17.4, 10.2 ,7.4Hz,1H),5.56(dd,J＝11.5,10.0Hz,1H),4.99(ddd,J＝17.1,1.9,1.2Hz,1H),4.90(ddd,J＝10.2,1.9,1.0Hz, 1H), 2.99 (ddd, J=4.6, 2.6, 1.3Hz, 1H), 2.68–2.45 (m, 1H), 2.00 (tdd, J=6.6, 6.1, 1.2Hz, 1H), 1.93–1.76 (m, ^2H ₎ . 130.16, 126.60, 115.15, 115.01, 112.71, 44.62, 41.45, 38.64, 33.06, 32.00ppm.

Experimental example 3

Catalytic generation: (3-(Z)-styryl-5-vinyl)cyclopentane-1,2-dimethanol

Under nitrogen protection, 23.1 mg (0.15 mmol) of norbornene dimethanol and 312.3 mg (3 mmol) of styrene were added to the reaction test tube, followed by adding 4.8 mg (4.5 μmol, 3.0 mol%) of the catalyst obtained in Example 1. 1 mL of THF (tetrahydrofuran) solution was stirred at room temperature for 4 h. After the reaction, the product was passed through a silica gel column (10% ethyl acetate in petroleum ether solution-60% ethyl acetate in petroleum ether solution) to finally obtain 34.5 mg of colorless oil (yield 89%), Z/E was 97: 3.

¹ H NMR (600 MHz, CDCl ₃ ) δ 7.34-7.27 (m, 2H), 7.25-7.16 (m, 3H), 6.46 (d, J=11.5 Hz, 1H), 5.73 (ddd, J=17.0, 10.1 ,7.8Hz,1H),5.51(dd,J＝11.5,10.0Hz,1H),5.11-4.88(m,2H),4.10-3.77(m,2H),3.66-3.55(m,3H),3.50( dd, J=11.5, 2.8Hz, 1H), 2.79–2.61 (m, 1H), 2.21–2.12 (m, 1H), 2.10 (dd, J=8.5, 4.0Hz, 2H), 1.98 (dt, J= 12.3, 6.0Hz, 1H), 1.35 (dt, J=12.4, 11.0Hz, 1H). ¹³ C NMR (151MHz, CDCl ₃ )δ141.46, 137.53, 135.90, 129.86, 128.59, 128.39, 126.82, 114.63, 61.93, 50.50 ,48.52,46.42,40.25,39.85ppm.

Experimental example 4

Catalytic production: (3-(Z)-4-fluorostyryl-5-vinyl)cyclopentane-1,2-dimethanol

Under nitrogen protection, 23.1 mg (0.15 mmol) of norbornene dimethanol and 366.2 mg (3 mmol) of 4-fluorostyrene were added to the reaction test tube, and then 4.8 mg (4.5 μmol, 3.0 mol%) of Example 1 was added. A solution of the catalyst in 1 mL of THF (tetrahydrofuran) was stirred at room temperature for 4 h. After the reaction, the product was passed through a silica gel column (10% ethyl acetate in petroleum ether solution-60% ethyl acetate in petroleum ether solution) to finally obtain 38.9 mg of colorless oil (yield 94%), Z/E was 98: 2.

¹ H NMR (600 MHz, CDCl ₃ ) δ 7.20-7.14 (m, 2H), 7.03-6.94 (m, 2H), 6.40 (d, J=11.5 Hz, 1H), 5.72 (ddd, J=17.0, 10.1 ,7.9Hz,1H),5.49(dd,J＝11.5,10.1Hz,1H),4.97(dddd,J＝23.1,10.1,1.8,0.8Hz,2H),3.79(s,2H),3.66–3.47( m, 4H), 2.71–2.57 (m, 1H), 2.25–2.13 (m, 1H), 2.12–2.07 (m, 2H), 2.01–1.92 (m, 1H), 1.33 (dt, J=12.4, 11.2 Hz, 1H). ¹³ C NMR (151MHz, CDCl ₃ )δ162.50,160.87,141.35,135.92,133.51,133.48,130.17,130.12,128.75,115.33,115.18,114.70,61.88,50.4,6,438.49ppm,438.48ppm .

Experimental example 5

Catalytic production: (Z)-4-hydroxy-2-butene-1-benzoate

Under nitrogen protection, 19.4 mg (0.12 mmol) of propylene benzoate and 22.4 mg (0.24 mmol) of Z-butene-1,4-diol were added, followed by adding dissolved 6.4 mg (6.0 μmol, 5.0 mol%) of Example 1 A solution of the obtained catalyst in 1 mL of THF (tetrahydrofuran) was stirred at 60° C. for 6 h. After the reaction, the product was passed through a silica gel column (10% ethyl acetate in petroleum ether solution-60% ethyl acetate in petroleum ether solution) to finally obtain 18.1 mg of colorless oil (yield 78.7%), Z/E was 98: 2.

¹ H NMR (600 MHz, CDCl ₃ ) δ 8.02 (ddd, J=4.4, 2.4, 1.2 Hz, 2H), 7.71-7.50 (m, 1H), 7.49-7.31 (m, 2H), 6.01-5.83 (m ,1H),5.79–5.59(m,1H),4.92(dd,J=7.0,1.3Hz,2H),4.32(dd,J=7.1,3.0Hz,2H),2.16(s,1H). ¹³ C NMR (151MHz, CDCl ₃ ) δ 166.76, 133.65, 133.21, 130.11, 129.73, 128.49, 125.71, 60.68, 58.62 ppm.

Experimental example 6

Catalytic production: (Z)-7-hydroxy-5-heptene-1-benzoate

Under nitrogen protection, 24.5 mg (0.12 mmol) of propylene benzoate and 22.4 mg (0.24 mmol) of Z-butene-1,4-diol were added, followed by adding dissolved 6.4 mg (6.0 μmol, 5.0 mol%) of Example 1 A solution of the obtained catalyst in 1 mL of THF (tetrahydrofuran) was stirred at 60° C. for 6 h. After the reaction, the product was passed through a silica gel column (10% ethyl acetate in petroleum ether solution-60% ethyl acetate in petroleum ether solution) to finally obtain 23.6 mg of colorless oil (yield 84.0%), Z/E was 97: 3.

¹ H NMR (400 MHz, CDCl ₃ ) δ 8.10-7.99 (m, 2H), 7.56 (ddd, J=6.9, 4.1, 1.4 Hz, 1H), 7.50-7.36 (m, 2H), 5.64 (dddd, J =9.4,6.5,4.7,3.2Hz,1H),5.58–5.43(m,1H),4.33(t,J=6.6Hz,2H),4.21(d,J=6.6Hz,2H),2.17(qd, J=7.4, 1.4Hz, 2H), 1.84–1.72 (m, 2H), 1.60 (s, 1H), 1.58–1.50 (m, 2H). ¹³ C NMR (151 MHz, CDCl ₃ ) δ 166.80, 132.99, 132.28, 130.45,129.63,129.21,128.44,64.84,58.60,28.29,27.02,26.00ppm.

Experimental example 7

Catalytic production: (Z)-12-hydroxy-10-dodecene-1-benzoate

Under nitrogen protection, 32.9 mg (0.12 mmol) of propylene benzoate and 22.4 mg (0.24 mmol) of Z-butene-1,4-diol were added, followed by adding dissolved 6.4 mg (6.0 μmol, 5.0 mol%) of Example 1 A solution of the obtained catalyst in 1 mL of THF (tetrahydrofuran) was stirred at 60° C. for 6 h. After the reaction, the product was passed through a silica gel column (10% ethyl acetate in petroleum ether solution-60% ethyl acetate in petroleum ether solution) to finally obtain 30.3 mg of colorless oil (yield 84.0%), Z/E was 98: 2.

¹ H NMR(400MHz, CDCl3)δ8.21-7.87(m,2H),7.76-7.53(m,1H),7.49-7.32(m,2H),5.64-5.57(m,1H),5.57-5.49( m, 1H), 4.31 (t, J=6.7Hz, 2H), 4.19 (d, J=6.3Hz, 2H), 2.07 (q, J=7.0Hz, 2H), 1.83–1.70 (m, 2H), 1.44(s, 1H), 1.38–1.27(m, 12H). ¹³ C NMR (101 MHz, CDCl ₃ ) δ 166.71, 133.21, 132.79, 130.56, 129.54, 128.38, 128.32, 65.12, 58.63, 29.58, 29.43, 29.37, ,29.16,28.72,27.42,26.01ppm.

Experimental example 8

Catalytic production: (Z)-5-(4'-nitrophenoxy)-2-penten-1-ol

Under nitrogen protection, 23.1 mg (0.12 mmol) of propylene benzoate and 22.4 mg (0.24 mmol) of Z-butene-1,4-diol were added, followed by adding dissolved 6.4 mg (6.0 μmol, 5.0 mol%) of Example 1 A solution of the obtained catalyst in 1 mL of THF (tetrahydrofuran) was stirred at 60° C. for 6 h. After the reaction, the product was passed through a silica gel column (10% ethyl acetate in petroleum ether solution-60% ethyl acetate in petroleum ether solution) to finally obtain 21.7 mg of colorless oil (yield 81.2%), Z/E was 92: 8.

¹ H NMR (400MHz, CDCl3) δ8.21 (dd, J=9.4, 2.7Hz, 2H), 7.08-6.79 (m, 2H), 5.98-5.88 (m, 1H), 5.83 (dd, J=12.4, 6.2Hz, 1H), 4.75 (d, J=6.0Hz, 2H), 4.37–4.25 (m, 2H), 1.53 (d, J=24.1Hz, 2H), 1.26 (d, J=2.7Hz, 1H) . ¹³ C NMR (101MHz, CDCl ₃ ) δ 163.80, 141.58, 131.74, 127.43, 125.94, 125.92, 114.45, 67.91, 58.44, 27.37ppm.

Experimental example 9

Catalytic production: (Z)-7-(4'-nitrophenoxy)-2-hepten-1-ol

Under nitrogen protection, 26.5 mg (0.12 mmol) of propylene benzoate and 22.4 mg (0.24 mmol) of Z-butene-1,4-diol were added, followed by adding dissolved 6.4 mg (6.0 μmol, 5.0 mol%) of Example 1 A solution of the obtained catalyst in 1 mL of THF (tetrahydrofuran) was stirred at 60° C. for 6 h. After the reaction, the product was passed through a silica gel column (10% ethyl acetate in petroleum ether solution-60% ethyl acetate in petroleum ether solution) to finally obtain 26.2 mg of colorless oil (yield 86.9%), Z/E was 91: 9.

¹ H NMR (400MHz, CDCl ₃ )δ8.59-8.00(m,1H),7.18-6.82(m,2H),5.77-5.64(m,1H),5.63-5.52(m,1H),4.24(d , J=6.6Hz, 2H), 4.07(t, J=6.4Hz, 2H), 2.23–2.14 (m, 2H), 1.92–1.80 (m, 2H), 1.65–1.53 (m, 2H), 1.32 ( s, 1H). ¹³ C NMR (101MHz, CDCl ₃ )δ164.11, 132.28, 129.10, 125.93, 114.39, 68.59, 58.57, 28.50, 27.02, 25.93ppm.

Experimental Example 10

Catalytic production: (Z)-2-(5'-hydroxy-3'-pentenyl)-isoindoline-1,3-dione

Under nitrogen protection, 24.1 mg (0.12 mmol) of propylene benzoate and 22.4 mg (0.24 mmol) of Z-butene-1,4-diol were added, followed by adding dissolved 6.4 mg (6.0 μmol, 5.0 mol%) of Example 1 A solution of the obtained catalyst in 1 mL of THF (tetrahydrofuran) was stirred at 60° C. for 6 h. After the reaction, the product was passed through a silica gel column (10% ethyl acetate in petroleum ether solution-60% ethyl acetate in petroleum ether solution) to finally obtain 23.2 mg of colorless oil (yield 83.5%), Z/E was 95: 5.

¹ H NMR (400 MHz, CDCl ₃ ) δ 7.87 (dd, J=5.4, 3.1 Hz, 2H), 7.74 (dd, J=5.5, 3.0 Hz, 2H), 5.87-5.65 (m, 1H), 5.64- 5.37(m, 1H), 4.17(t, J=5.1Hz, 2H), 3.79(t, J=7.1Hz, 2H), 2.53(qd, J=7.4, 1.5Hz, 2H), 1.47(s, 1H ). ¹³ C NMR (101MHz, CDCl ₃ )δ168.40,133.99,132.04,131.70,127.99,123.26,58.32,37.49,26.54ppm.

Experimental Example 11

Catalytic production: (Z)-2-(7'-hydroxy-5'-heptenyl)-isoindoline-1,3-dione

Under nitrogen protection, 27.5 mg (0.12 mmol) of propylene benzoate and 22.4 mg (0.24 mmol) of Z-butene-1,4-diol were added, followed by adding dissolved 6.4 mg (6.0 μmol, 5.0 mol%) of Example 1 A solution of the obtained catalyst in 1 mL of THF (tetrahydrofuran) was stirred at 60° C. for 6 h. After the reaction, the product was passed through a silica gel column (10% ethyl acetate in petroleum ether solution-60% ethyl acetate in petroleum ether solution) to finally obtain 27.9 mg of colorless oil (yield 89.6%), Z/E was 98: 2.

¹ H NMR (400 MHz, CDCl ₃ ) δ 7.86 (dd, J=5.4, 3.1 Hz, 2H), 7.77-7.64 (m, 2H), 5.71-5.60 (m, 1H), 5.58-5.38 (m, 1H) ), 4.23 (d, J=6.8Hz, 2H), 3.75–3.65 (m, 2H), 2.18 (qd, J=7.4, 1.5Hz, 2H), 1.77–1.65 (m, 2H), 1.47 (p, J=7.3Hz, 2H). ¹³ C NMR (101MHz, CDCl ₃ ) δ 169.18, 134.63, 132.84, 129.90, 123.93, 59.20, 38.29, 28.46, 27.26, 27.10ppm.

Experimental example 12

Catalytic production: (Z)-4-(7'-hydroxy-5'-heptene-1'-oxy)benzaldehyde

Under nitrogen protection, 24.1 mg (0.12 mmol) of propylene benzoate and 22.4 mg (0.24 mmol) of Z-butene-1,4-diol were added, followed by adding dissolved 6.4 mg (6.0 μmol, 5.0 mol%) of Example 1 A solution of the obtained catalyst in 1 mL of THF (tetrahydrofuran) was stirred at 60° C. for 6 h. After the reaction, the product was passed through a silica gel column (10% ethyl acetate in petroleum ether solution-60% ethyl acetate in petroleum ether solution) to finally obtain 24.3 mg of colorless oil (yield 86.4%), Z/E was 97: 3.

¹ H NMR (400 MHz, CDCl ₃ ) δ 9.88 (d, J=8.9 Hz, 1H), 8.23-7.68 (m, 2H), 6.99 (dd, J=8.8, 2.2 Hz, 2H), 5.78-5.62 ( m, 1H), 5.60–5.49 (m, 1H), 4.22 (t, J=5.6Hz, 2H), 4.04 (t, J=6.3Hz, 2H), 2.17 (q, J=7.3Hz, 2H), 1.88–1.78(m, 2H), 1.62–1.49(m, 2H). ¹³ C NMR (101 MHz, CDCl ₃ ) δ 190.89, 164.17, 132.23, 132.03, 129.81, 129.11, 114.75, 68.13, 58.52, 28.56, 27.05, 25 ppm.

Experimental Example 13

Catalytic production: methyl 4-[(3'Z)-5'-hydroxy-3'-pentene-1'-oxy]benzoate

Under nitrogen protection, 24.7 mg (0.12 mmol) of propylene benzoate and 22.4 mg (0.24 mmol) of Z-butene-1,4-diol were added, followed by adding dissolved 6.4 mg (6.0 μmol, 5.0 mol%) of Example 1 A solution of the obtained catalyst in 1 mL of THF (tetrahydrofuran) was stirred at 60° C. for 6 h. After the reaction, the product was passed through a silica gel column (10% ethyl acetate in petroleum ether solution-60% ethyl acetate in petroleum ether solution) to finally obtain 24.0 mg of colorless oil (yield 84.7%), Z/E was 98: 2.

¹ H NMR (400MHz, CDCl ₃ )δ8.15-7.84(m,2H),7.05-6.81(m,2H),5.97-5.77(m,1H),5.76-5.49(m,1H),4.26(d , J=6.6Hz, 2H), 4.06(t, J=6.4Hz, 2H), 3.90(s, 3H), 2.75–2.55(m, 2H), 1.61(s, 1H). ¹³ C NMR(101MHz, CDCl ₃ )δ166.86,162.45,131.63,131.48,128.01,122.75,114.05,67.15,58.39,51.90,27.46ppm.

Experimental Example 14

Catalytic production: methyl 4-[(5'Z)-7'-hydroxy-3'-heptene-1-oxy]benzoate

Under nitrogen protection, 28.1 mg (0.12 mmol) of propylene benzoate and 22.4 mg (0.24 mmol) of Z-butene-1,4-diol were added, followed by adding dissolved 6.4 mg (6.0 μmol, 5.0 mol%) of Example 1 A solution of the obtained catalyst in 1 mL of THF (tetrahydrofuran) was stirred at 60° C. for 6 h. After the reaction, the product was passed through a silica gel column (10% ethyl acetate in petroleum ether solution-60% ethyl acetate in petroleum ether solution) to finally obtain 24.5 mg of colorless oil (yield 77.4%), Z/E was 96: 4.

¹ H NMR (400MHz, CDCl ₃ ) δ 8.25-7.85 (m, 2H), 6.99-6.82 (m, 2H), 5.73-5.64 (m, 1H), 5.58 (dt, J=11.0, 7.2Hz, 1H ),4.23(d,J＝6.6Hz,2H),4.03(t,J＝6.4Hz,2H),3.90(s,3H),2.19(q,J＝7.4Hz,2H),1.83(dd,J =9.0,6.2Hz,2H),1.62-1.50(m,2H),1.36(s,1H). 13CNMR( ^101MHz , _CDCl3 )δ166.92,162.85,132.33,131.59,129.04,122.44,114.06,67.90,58.55 ,51.84,28.63,27.08,26.02ppm.

Experimental example 15

Catalyst Thermal Stability Test

The catalyst I obtained by the present invention and the catalysts D and E reported by the inventors were tested for thermal stability under the same conditions, that is, anthracene was used as the internal standard, and ¹ H NMR was used at 55°C to monitor the stability of catalysts I, D, and E at 55°C. Decomposition in THF-d8. Wherein the structural formulas of catalysts D and E are respectively:

9.8 mg of catalysts D, E and I were loaded into the nuclear magnetic tube, then 3.6 mg (0.02 mmol) of the internal standard anthracene was added, and 0.5 mL of anhydrous deuterated tetrahydrofuran (THF-d8) was added to the nuclear magnetic tube. The hydrogen spectra of the three catalysts were continuously tested every 30 min in a Bruker NMR instrument at a temperature of 55 °C. The decomposition rate of the catalyst was determined by monitoring the peak areas of the hydrogen atoms on the carbene carbon and the internal standard.

The results are shown in Figure 1: Catalyst I obtained by the present invention has the slowest decomposition rate relative to catalysts D and E, indicating that the thermal stability of catalyst I obtained by the present invention is greatly improved.

To sum up, the 2,4,5,7-tetrabromo-1,8-naphthalene dithiol ruthenium carbene catalyst provided by the present invention can obtain the product Z/E ratio in the catalytic olefin metathesis reaction as high as 99:1, and the yield is as high as 99:1. 95%, has the characteristics of good stability, high reactivity, strong Z-form selectivity and high yield. The invention overcomes the shortcomings of low catalyst activity and poor Z-selectivity in the research on Z-selective olefin metathesis catalysis in the prior art, and has a good application prospect.

The above-mentioned embodiments are only preferred embodiments of the present invention, and cannot be used to limit the scope of protection of the present invention. Any insubstantial changes and substitutions made by those skilled in the art on the basis of the present invention belong to the scope of the present invention. Scope of protection claimed.

Claims (4)

1. a preparation method of Z -selective ruthenium carbene olefin metathesis catalyst, is characterized in that, comprises the following steps:

in:

Under nitrogen, combine Hoveyda catalyst (A) with 2,4,5,7-tetrabromo-1,8-dimercaptozinc salt (B) or 2,4,5,7-tetrabromo-1,8-bis Sodium thiosulfate (C) is dissolved in organic solvent, vacuum-dried after stirring, centrifuged after adding methylene chloride, and solvent is removed to obtain final product—— Z -selective ruthenium carbene olefin metathesis catalyst, and this final product has the general structural formula I; wherein Mes is 2,4,6-trimethylphenyl. 2. the preparation method of Z -selectivity ruthenium carbene olefin metathesis catalyst as claimed in claim 1, is characterized in that, described organic solvent is tetrahydrofuran. 3. the preparation method of Z -selective ruthenium carbene olefin metathesis catalyst as claimed in claim 1, is characterized in that, described stirring temperature is ^{0 ℃} , time 0.5 h. 4. the application of the Z-selective ruthenium carbene olefin metathesis catalyst prepared by the method as claimed in claim 1 in the preparation of Z -form olefin product by catalyzing ruthenium carbene olefin metathesis reaction.

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