Bachelorprüfung

Organische Chemie III

529-0232-00J

Prof. Dr. E. M. Carreira

14th August 2014

Name: ________________________________________________________________

Legi-Nr: ______________________________________________________________

Degree/Major: _____________________________________________________

Please read the questions caref ully.

Answer each question on a new sheet of paper. Account for your answers
brief ly with keywor ds.
Make sure you writ e your name and Legi- Nr. on ever y page.

Durat ion: 60 m inutes

Note: Unreadable or ambig uous answers will not be graded!

Question 1 Question 2 Question 3 Question 4 Question 5

Points

Total points: ______ grade: ______

Question 1 (10 points)
In 2003, O’Brien reported the diastereoselective reaction of carbamate 1 with mCPBA. Depending on
the nature of R (H or p-Ns) either product 2 or 3 was obtained selectively.

a) Predict the structure of the major product obtained for R = H and for R = p-Ns, respectively.

b) Give a detailed explanation for the observed outcome by a drawing of the transition states
leading to 2 and 3.

Bull reported the epoxidation of 4 with catalytic VO(acac)2 and stoichiometric t-BuOOH to give
intermediate 5. Upon work-up of the reaction mixture, 6 was obtained.

c) Please give the configuration of 5 at the indicated stereocenter.

d) Explain the stereochemical outcome of the reaction 4→5 with a drawing of the transition
state. Comment on the crucial interactions.
Question 2 (10 points)
In 1987, Chamberlin reported a method for the stereoselective synthesis of 2,5-disubstituted
tetrahydrofurans 8/9 from the corresponding keto-epoxide 7. Depending on the conditions, either
the cis or the trans isomer could be obtained as the major product.

a) Suggest a mechanism for this transformation.

b) Based on this mechanistic proposal, provide an explanation for the different stereochemical
outcomes observed with the two sets of reaction conditions.
Question 3 (10 points)
In 1982, Tsuji and co-workers reported the following reaction of allylic alcohol 10:

Hint: The acetal does not react under these conditions.

a) Please provide the structures of 11 and 12 without stereochemical information. Provide

mechanisms for the transformations. What is the name of the reaction from 11 to 12?

b) Predict the configuration of all new stereogenic centers. Support your answer with
appropriate models highlighting crucial interactions.
Question 4 (10 points)
In a study of conjugate additions to α,β-unsaturated esters 13 with an allylic stereocenter, an
interesting switch in face-selectivity was observed:

a) Please provide an explanation for the selectivity in the two cases by drawing appropriate
3D models and highlighting important interactions.
Question 5 (10 points)
In 1982, Evans reported the sequence of reactions shown below as part of a highly stereocontrolled
synthesis of (+)-Prelog-Djerassi Lactonic Acid.

a) Give the structure of intermediate 17.

b) Predict the configuration of the stereocenter marked with an asterisk for the major
diastereomer of 18.

c) Give the structure of intermediate 20.

d) Predict the configuration of the stereocenters marked with an asterisk in structure 21.

e) Propose a three-dimensional transition state model for the reaction of 20 and 19 to give 21
and highlight crucial features that lead to high stereocontrol.