You are on page 1of 12

Name:

Chemistry 51 S12
Exam #3
May 23, 2012

Please put your name on all pages (including scratch). Do not wait until
after the end of the exam to do this. Students who wait until after time
has been called have an unfair advantage by gaining extra time.
This exam has 6 questions, 2 cover pages, 6 exam pages, and 4 scratch
pages (total 12 pages).
Under no circumstances will answers on scratch paper be graded.
Save and turn in (staple) all scratch papers at the end of the exam.
120 minutes have been allotted for completion of the exam.
The Dartmouth Honor Principle is in effect.

*Note*
When providing written explanations, incorrect
statements interspersed among correct answers
will result in deduction of points.
You are to assume that formal charges should
be included for all appropriate structures.

Name:

1. _____ (36)
2. _____ (24)
3. _____ (20)
4. _____ (15)
5. _____ (25)
6. _____ (25)

Total: __________ (145)

Name:
1. Please indicate the starting materials and all reagents required to prepare the given products. (36 pts).

Name:
2. Predict only the major product of each reaction. State whether each reaction will proceed
predominantly via an SN2, E2, or SN1/E1 mechanism. It is possible for there to be no reaction.
For reactions undergoing SN1/E1 mechanisms, draw both products. When needed, please address all stereochemical issues using wedges and hashes. (24 pts)

Name:
3a. Allenylidenes, such as A, can be prepared from the corresponding alkyne in the reaction
illustrated below. Using curved-arrow formalism, propose a reasonable mechanism. (Hint
This reaction does not proceed through a carbocationic intermediate). (10 pts)

3b. The Grob fragmentation, shown below, is a method for synthesizing medium-sized rings
from two smaller ones. Using curved-arrow formalism, propose a reasonable mechanism. (Hint
This reaction also does not proceed through a carbocationic intermediate). (10 pts)

Name:
4. Eiichi Negishi won the Nobel Prize in Chemistry in 2010 for discovering the reaction
illustrated below. He shared the award with Akira Suzuki (discovered the SuzukiMiyaura cross-coupling reaction) and with Richard Heck (responsible for the Heck
reaction). Please propose a plausible mechanism for the Negishi cross-coupling reaction by providing a likely catalytic cycle. Arrow formalism is NOT required. (Hint This
transformation is entirely analogous to the mechanism of the SuzukiMiyaura crosscoupling reaction). (15 pts)

Name:
5. Please provide a selective synthesis for the molecule shown in the square under the
given constraints. Use retrosynthetic analysis to aid your thinking (you do not have to
show the retrosynthesis), but then write your synthesis in the forward direction. ONLY
the synthesis in the forward direction will be graded. Indicate all reagents used. Mechanisms are not necessary. All organometallic and cross-coupling reagents should be
made and all inorganic reagents are allowed. In your carbon count, you should not include Cs on cross-coupling reagents which do not appear in the final product. (25 pts)

Name:
6. Please provide a selective synthesis for the molecule shown in the square under the
given constraints. Use retrosynthetic analysis to aid your thinking (you do not have to
show the retrosynthesis), but then write your synthesis in the forward direction. ONLY
the synthesis in the forward direction will be graded. Indicate all reagents used. Mechanisms are not necessary. All organometallic and cross-coupling reagents should be
made and all inorganic reagents are allowed. In your carbon count, you should not include Cs on cross-coupling reagents which do not appear in the final product. (25 pts)

Name:
Scratch Sheet 1

Name:
Scratch Sheet 2

10

Name:
Scratch Sheet 3

11

Name:
Scratch Sheet 4

12