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. 2021;32(6):601-604.
doi: 10.1055/a-1308-0370. Epub 2020 Nov 10.

Stereoselective Synthesis of (4 S,5 S)-5-Vinyloxazolidin-2-one-4-carboxylate as a β-Vinylserine Synthetic Equivalent by Vinyl Grignard Addition to an N-Tosyl Version of Garner's Aldehyde

Ernest G Nolen  1 , Yuqi M Cao  1 , Brynn D Lewis  1 , Madison H Powers  1 , Andrew W Thompson  1 , John M Bennett  1
Affiliations

Stereoselective Synthesis of (4 S,5 S)-5-Vinyloxazolidin-2-one-4-carboxylate as a β-Vinylserine Synthetic Equivalent by Vinyl Grignard Addition to an N-Tosyl Version of Garner's Aldehyde

Ernest G Nolen et al. Synlett. 2021.

Abstract

A highly efficient synthesis of a β-vinylserine synthetic equivalent is reported that exploits the stereodirecting effect of the N-toluenesulfonamide in an anti-diastereoselective (8.5:1) vinyl Grignard addition to an analogue of Garner's aldehyde. Both aryl and alkyl Grignards are shown to give increased anti-selectivity compared with N-Boc Garner's aldehyde.

Keywords: Garner aldehyde; alkenyl amino acid; oxazolidinones; vinylserine.

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Figures

Scheme 1
Scheme 1
Target β-vinylserine (β-VSer) synthetic equivalent 1 and precursor
Scheme 2
Scheme 2
Approaches to cis-oxazolidinones
Scheme 3
Scheme 3
Synthesis of β-VSer derivatives 12 and 14; pNs = 4-O2NC6H4SO2.
Scheme 4
Scheme 4
Felkin–Anh depiction of nucleophilic attacks
See this image and copyright information in PMC

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