CHEM 5000 Homework 2 (Due Nov.

14th)
1. Draw the most stable conformation of the following molecules

2. a) using “arrow-pushing” convention, outline a reasonable mechanism for the

following transformation:

b) “this reaction is thermodynamically controlled” explain what is implied by this

statement.

c) draw the most stable conformations of compounds 2 and 3, on the basis of the
statement in b), predict which is the major product of the reaction shown above, and
explain what factors make it the thermodynamic product.

3. The diastereoselectivity of alkyl radical addition to substituted alkylidene malononitriles is a

function of the size of the attacking radical when there is a bulky substituent at the -carbon.
Conformational analysis of the reactant indicates that it prefers conformation a over b by 3.0
kcal/mol. Suggest a TS structure, showing reactant conformation and reagent trajectory that is in
accord with these results. Use the Curtin-Hammet principle (p. 296) to construct a reaction energy
diagram that illustrates the product composition in terms of TS energy.
4. The A vaule of -CH3 in mono substituted cyclohexane is about 1.74 kacal/mol while for H it
would be 0. But in N-substituted piperidine derivatives, the A value for H would be 0.36 kcal/mol.
For -CH3, the A value could be up to 3.0 kcal/mol. Please explain this observation.

5. Explain why the exchange for deuterium of the proton of HC(CF3)3 catalyzed by MeONa in
MeOD is 109 times faster than the exchange reaction of the proton of HCF3 under the same
condition (start from writing down a chemical reaction according to the above description).

6. A mechanism for alkene arylation catalyzed by Pd(II) is outlined below. The isotope effect
kH/kD was found to be 5 when benzene-d6 was used. There was no isotope effect when styrene-β-
d2 was used. Which steps in the reaction mechanism could be rate determining, given this
information on isotope effects?

7. refer to textbook, Carey & Sundberg Advanced Organic Chemistry (Part A) Chapter 2: 2.26