Asymmetric induction in the Claisen rearrangement of N-allylketene N,O-acetals

Mark J. Kurth, Owen H W Decker, Hakon Hope, Michael D. Yanuck

Research output: Contribution to journalArticlepeer-review

65 Scopus citations

Abstract

Asymmetric C-C bond formation via the diastereoselective aza-Claisen rearrangement of N-allylketene N,O-acetal 1 is described. Diastereoselection noted for rearrangement 1 → 2 ranges from 84% to 96% and is a consequence of complete (Z)-N,O-acetal olefin selectivity in 1, high Cα-si-face selectivity in the rearrangement of 1 to 2, and the absence of Cα epimerization in oxazoline 2. Experiments which establish the steric bulk of the C4 appendage as a particularly important variable are also reported. Acid-catalyzed hydrolysis of rearranged oxazoline 2 completes an efficient, enantioselective synthesis of 2-substituted pent-4-enoic acid 4 and regenerates for recycling the chiral auxiliary reagent 3, initially prepared from inexpensive α-amino acids.

Original languageEnglish (US)
Pages (from-to)443-448
Number of pages6
JournalJournal of the American Chemical Society
Volume107
Issue number2
StatePublished - 1985

ASJC Scopus subject areas

  • Chemistry(all)

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