1. Rearrangement Reactions (1/3)

Question 1

Give the generalised mechanism for the Baeyer-Villiger rearrangement.

Answer 1

C-C bond breaks, 1-2 migration.

Question 2

Give the generalised mechanism for the Beckmann rearrangement.

Answer 2

C-C bond breaks, 1-2 migration.

Question 3

Give the mechanism for the following Beckmann rearrangement in the context of nylon production.

Answer 3

Question 4

What can be said about molecular orbital overlap during the 1,2- migration in Beckmann rearrangement?

Answer 4

1. C–C and N–O bonds antiperiplanar (overlap between σC–C and σ*N–O).
2. Retention of the stereochemistry during 1,2-migration.

Question 5

Answer 5

Question 6

Outline the following Beckmann rearrangement and indicate the issues of fragmentation.

Answer 6

Question 7

Outline what oxidants may be used in the Baeyer-Villiger rearrangement.

Answer 7

Question 8

Outline the best to worst migrating groups for 1,2-rearrangement in the Baeyer-Villiger.

Answer 8

1. C–C and O–O bonds antiperiplanar
   (overlap between σC–C and σ*O–O)
2. Retention of the stereochemistry
   during 1,2-migration

Question 9

Outline the regioselectivity that governs the 1,2-rearrangement in the Baeyer-Villiger reaction.

Answer 9

Question 10

Give the product(s) of the following Baeyer-Villiger rearrangement.

Answer 10

Question 11

Answer 11

Question 12

Draw curly arrows for all steps of the following mechanism.

Answer 12

Question 13

Draw curly arrows for all steps of the following mechanism.

Answer 13