Stereoselective beta-hydroxy-alpha-amino acid synthesis via an ether-directed, palladium-catalysed aza-Claisen rearrangement

Fanning, K. N., Jamieson, A. G. and Sutherland, A. (2005) Stereoselective beta-hydroxy-alpha-amino acid synthesis via an ether-directed, palladium-catalysed aza-Claisen rearrangement. Organic and Biomolecular Chemistry, 3, pp. 3749-3756. (doi: 10.1039/b510808j) (PMID:16211111)

Abstract

A highly diastereoselective synthesis of (2S,3S)-β-hydroxy-α-amino acids has been developed from enantiopure α-hydroxy acids using a MOM-ether-directed, palladium(II)-catalysed, aza-Claisen rearrangement of allylic acetimidates to effect the key step. This highly stereoselective process gave allylic amides in diastereomeric ratios of up to 14 : 1. Problems associated with the isolation of 1,3-products (anti-Claisen) from sterically demanding substrates via an insitu palladium(0)-catalysed rearrangement process were overcome by the addition of a re-oxidant, p-benzoquinone, leading to cleaner reactions and improved yields of the 3,3-products (Claisen). The target β-hydroxy-α-amino acids are an important class of natural products that are also components of more complex organic compounds with significant biological properties.

• Item Type: Articles
• Status: Published
• Refereed: Yes
• Glasgow Author(s) Enlighten ID: Jamieson, Professor Andrew and Sutherland, Professor Andrew
• Authors: Fanning, K. N., Jamieson, A. G., and Sutherland, A.
• College/School: College of Science and Engineering > School of Chemistry
• Journal Name: Organic and Biomolecular Chemistry
• Publisher: Royal Society of Chemistry
• ISSN: 1477-0520
• ISSN (Online): 1477-0539
• Published Online: 09 September 2005