Racemization in the use of N-(9-(9-phenylfluorenyl))serine-derived cyclic sulfamidates in the synthesis of delta-keto alpha-amino carboxylates and prolines.

[reaction: see text]Ring opening of enantiopure N-(9-(9-phenylfluorenyl)serine-derived cyclic sulfamidates with beta-keto esters, beta-keto ketones, and dimethyl malonate gave a variety of gamma-substituted amino acid analogues in racemic form. Investigation of the mechanism for racemization revealed that beta-elimination occurred to form a dehydroalanine intermediate that underwent subsequent Michael addition.