Flash vacuum pyrolysis of stabilised phosphorus ylides. Part 17. Preparation of aliphatic amino acid derived γ-alkoxycarbonylamino-β-oxo ylides and pyrolysis to give α,β-acetylenic-γ-amino acid and GABA analogues

R A Aitken, N Karodia, Tracy Massil, R J Young

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25 Citations (Scopus)

Abstract

A series of eleven alpha-aminoacyl stabilised phosphorus ylides 9-19 have been prepared by condensation of N-alkoxycarbonyl protected amino acids with Ph3P=CHCO2Et using a carbodiimide peptide coupling reagent. Upon ash vacuum pyrolysis at 600 degreesC, these undergo extrusion of Ph3PO to give the corresponding, alpha,beta-acetylenic gamma-amino esters 21-29, 33 and 34 in moderate yield. In two cases the terminal alkynes 30 and 31 are also formed. The beta-aminoacyl ylide 20 from beta-alanine similarly gives the alpha,beta-acetylenic delta-amino ester 35 upon pyrolysis. Regioselective addition of HBr to the triple bond of one acetylenic ester 25 was observed giving a mixture of E and Z alpha-bromoacrylates 36. Hydrogenation of the N-Cbz acetylenic esters 21-23 and 33 results in N-deprotection and hydrogenation of the triple bond to afford the chiral GABA analogues 37-40 in 70 --> 95% ee as determined by F-19 NMR of their Mosher amides. Fully assigned C-13 NMR spectra of all the ylides and acetylenic ester derivatives are presented.

Original languageEnglish
Pages (from-to)533-541
Number of pages9
JournalJournal of the Chemical Society, Perkin Transactions 1
Issue number4
DOIs
Publication statusPublished - Jan 2002

Keywords

  • STEREOSPECIFIC SYNTHESIS
  • DERIVATIVES
  • MECHANISM
  • FACILE

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