Enantioselective synthesis of alkylidene cyclohexanes by an asymmetric olefination/cross‐coupling sequence

Scott E. Denmark, Chien‐Tien ‐T Chen

Research output: Contribution to journalArticle

Abstract

A general method for the preparation of dissymmetric olefins has been developed. The anion derived from an enantiomerically enriched P‐(phenylthiomethyl)phosphonamidate(1,3,2‐oxazaphosphorinane2‐oxide) was added to 4‐tert‐butylcyclohexanone with excellent diastereoselectivity. The β‐hydroxyphos‐phonamidate was converted into a (phenylthio)‐methylidene with excellent stereospecificity using a novel electrophile‐promoted olefination that employed trityl triflate and 2,6‐lutidine in warm acetonitrile. The vinyl sulfide underwent nickel‐catalyzed coupling with Grignard and dialkylzinc reagents to produce (S)‐4‐(tert‐butyl)alkylidenecyclohexanes with moderate to high stereospecificity.

Original languageEnglish (US)
Pages (from-to)133-144
Number of pages12
JournalHeteroatom Chemistry
Volume6
Issue number2
DOIs
StatePublished - Jan 1 1995

ASJC Scopus subject areas

  • Chemistry(all)

Fingerprint Dive into the research topics of 'Enantioselective synthesis of alkylidene cyclohexanes by an asymmetric olefination/cross‐coupling sequence'. Together they form a unique fingerprint.

  • Cite this