Diastereo- and enantioselective synthesis of nitroso Diels-Alder-type bicycloketones using dienamine: Mechanistic insight into sequential nitroso aldol/Michael reaction and application for optically pure 1-amino-3,4-diol synthesis

Norie Momiyama, Yuhei Yamamoto, Hisashi Yamamoto

Research output: Contribution to journalArticlepeer-review

114 Citations (Scopus)

Abstract

This article presents complete diastereo- and highly enantioselective synthesis of nitroso Diels-Alder-type bicycloketones using dienamine. With the hydrogen bonding of two hydroxyls in the bulky binaphthol 1c, high enantioselectivities and complete diastereoselectivity are realized in 2-oxa-3-aza-bicycloketone synthesis. On the other hand, α,β- unsaturated ketone can be employed as diene precursor, utilizing readily available tetrazole catalyst 3b, to provide the 3-oxa-2-aza-bicycloketones in moderate yields with complete enantioselectivities. Investigation into the reaction utilizing 2-morpholino-4,4-diphenylcyclohexadiene 2d clearly indicated that cyclization with the bulky binaphthol 1c is involved in the sequential process, the N-nitroso aldol reaction, followed by Michael addition. In addition, optically pure 1-amino-3,4-diol is synthesized from 2-oxa-3-aza-bicycloketones. Use of p-phenoxynitrosobenzene allows access to protected amino diol via cleavage of the N-Ph bond.

Original languageEnglish
Pages (from-to)1190-1195
Number of pages6
JournalJournal of the American Chemical Society
Volume129
Issue number5
DOIs
Publication statusPublished - 2007 Feb 7

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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