Conversion of L-Cysteine into D-α-Amino Acids and Related Transformations

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Errata

This article is corrected by:

  1. Errata: Conversion of L-Cysteine into D-α-Amino Acids and Related Transformations Volume 2011, Issue 36, 7419, Article first published online: 23 November 2011

Abstract

Naturally configured cysteine is converted into 4-substituted thiazolidines via the 4-carbaldehyde corresponding to the serine derived Garner's aldehyde. The key transformation is the conversion into 5-thiazolidinones by 1O2 oxidation, and fragmentation of the primary 5-hydroperoxides under in situ acetylating conditions. Whereas the reagent couple trimethylsilyl halides/phenol selectively cleaves the N-Boc group, LiOH/H2O2 transforms the thiol lactones into lactones by an unknown mechanism, and, subsequently, also cleaves the acetonide affording N-Boc-protected D-amino acids without loss of optical activity. This sequence tolerates unsaturated residues with sensitive allylic functions. In some cases, double bond isomerization is, however, observed. Thethiazolidine intermediates can be cleaved with 3-nitro-2-pyridinesulfenyl chloride, giving reactive mixed disulfides.

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