The document summarizes the sections and questions on the CH 442 Mid-Term Exam for Spring 2022. It includes:
1) Showing major organic products for 8 out of 9 reactions and showing stereochemistry where relevant.
2) Providing detailed mechanisms for 2 out of 4 reactions.
3) Using frontier molecular orbital theory and Mobius-Huckel/orbital topology models to determine if a transformation is allowed suprafacially.
4) Explaining the "inverse electron demand" Diels-Alder reaction using frontier molecular orbital theory.
5) Deriving molecular orbitals for cyclobutadiene and explaining reactions involving cyclobutadiene
The document summarizes the sections and questions on the CH 442 Mid-Term Exam for Spring 2022. It includes:
1) Showing major organic products for 8 out of 9 reactions and showing stereochemistry where relevant.
2) Providing detailed mechanisms for 2 out of 4 reactions.
3) Using frontier molecular orbital theory and Mobius-Huckel/orbital topology models to determine if a transformation is allowed suprafacially.
4) Explaining the "inverse electron demand" Diels-Alder reaction using frontier molecular orbital theory.
5) Deriving molecular orbitals for cyclobutadiene and explaining reactions involving cyclobutadiene
The document summarizes the sections and questions on the CH 442 Mid-Term Exam for Spring 2022. It includes:
1) Showing major organic products for 8 out of 9 reactions and showing stereochemistry where relevant.
2) Providing detailed mechanisms for 2 out of 4 reactions.
3) Using frontier molecular orbital theory and Mobius-Huckel/orbital topology models to determine if a transformation is allowed suprafacially.
4) Explaining the "inverse electron demand" Diels-Alder reaction using frontier molecular orbital theory.
5) Deriving molecular orbitals for cyclobutadiene and explaining reactions involving cyclobutadiene
The document summarizes the sections and questions on the CH 442 Mid-Term Exam for Spring 2022. It includes:
1) Showing major organic products for 8 out of 9 reactions and showing stereochemistry where relevant.
2) Providing detailed mechanisms for 2 out of 4 reactions.
3) Using frontier molecular orbital theory and Mobius-Huckel/orbital topology models to determine if a transformation is allowed suprafacially.
4) Explaining the "inverse electron demand" Diels-Alder reaction using frontier molecular orbital theory.
5) Deriving molecular orbitals for cyclobutadiene and explaining reactions involving cyclobutadiene
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CH 442 Mid-Term Exam Spring 2022
Sign the Honor Code upon completion of the exam.
I. Show the Major Organic Product for 8 out of 9 of the Following Reactions. Show stereochemistry where relevant (5 points each, 40 total) 1. O
heat
2.
3.
hv 4.
5.
6. 7.
8. heat
9. II. Show Detailed mechanisms for 2 out of 4 of the following reactions (8 pts each, 16 total). 1. 2. (hint: Only “6 e-“ reactions for pericyclic steps, and keto enol tautomerism requires a mechanism)
OH O H3C CH3 H3C CH3 heat 3. O CH3 CH3 14C hv 14C 14C - CH3 C O + C O CH3 C CH3 CH3 N +
N 50:50 mixture
4.
hv + HC CH III. Use the rationale and formalism of 2 of the models which we studied (frontier molecular orbital theory, and Mobius-Huckel/orbital topology) to determine whether the following transformation is allowed suprafacially. The answer to this should take the form of two separate answers(16 pts) hv IV. The Diels-Alder Reaction usually occurs between an electron-deficient dienophile and an electron-rich diene. The “inverse electron demand” Diels-Alder reaction, between electron- deficient dienes and electron-rich dienophiles is also known. Show why this reaction occurs using Frontier Molecular Orbital theory, keeping in mind both the symmetry of the involved orbitals, as well as their relative potential energy. (10 pts)
V. Cyclobutadiene has long intrigued chemists, as the ultimate example of antiaromatic
hydrocarbons. As such, for many years it could only be isolated in an Ar matrix at 4-8 K.
1. Derive the p/molecular orbitals for cyclobutadiene, showing the correct number of orbitals, the sign/shading of the orbitals, the relative potential energy of the orbitals, and the electron configuration of the Pi system of the molecule. (6 points) In contrast, its organometallic complex, cyclobutadieneiron tricarbonyl (henceforth “CBIT”) is isolable and storable under normal laboratory conditions. I’ve got a gram of this stuff in my freezer!
“CBIT”
2. The precursor to CBIT, dichlorocyclobutene, is made through the following series of
reactions. Deduce the structure of X. (5 pts) Cyclobutadiene can be generated upon oxidation of CBIT and trapped in subsequent reactions. This strategy was used by the Snapper Group at Boston College, and it figures prominently in their synthesis of Asteriscanolide, two key steps of which are shown below:
3. In the conversion of A to B, the trimethylamine oxide simply oxidizes the iron, to
generate the uncomplexed cyclobutadiene derived from A. Show a detailed mechanism for the conversion of this species to B. There is no need to wrestle with the mechanism of the oxidation, just what happens afterwards.(5 pts) Bonuses: You may get credit for either A or B, whichever gives you more credit.
A. Easy fun Bonus (1 point): I'm bringing back an old favorite here, with a twist.....tell me something I don't know about Middlebury College....eg, its people, places, trivia, non-nasty gossip.....However, given that you are all upperclasspersons, I will only give credit for this info if I've never heard it before....no substitutes accepted!
B. (5 points) If you browsed the Woodward paper I put on reserve in the Armstrong library, tell me the type of “experiment” they were doing when they got the result that piqued interest in pericyclic reactions.
