Stereoselective E and Z Olefin Formation by Wittig Olefination of Aldehydes with Allylic Phosphorus Ylides. Stereochemistry

Rui Tamura, Koji Saegusa, Masato Kakihana, Oda Daihei

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79 Citations (Scopus)

Abstract

Sterically crowded allylic tributylphosphorus ylides such as β,α-disubstituted allylic ylides react with various aldehydes to afford E olefins with high stereoselectivity (E > 92%). As the steric demand of the ylides was decreased, bulky aldehydes were required to achieve high E selectivity. On the other hand, predominant or exclusive formation of Z olefins was achieved by using allylic triphenylphosphorus ylides and tertiary aldehydes like pivaldehyde, while the combination of allylic triphenylphosphorus ylides and such large secondary aldehydes as cyclohexanecarboxaldehyde led to E olefin formation under the lithium salt free conditions. The distinct lithium salt effect was observed in the reaction effected with triphenylphosphorus ylides. The origin of the observed E or Z selectivity can be reasonably explained according to Vedejs’ rationale on the Wittig reaction stereochemistry.

Original languageEnglish
Pages (from-to)2723-2728
Number of pages6
JournalJournal of Organic Chemistry
Volume53
Issue number12
DOIs
Publication statusPublished - 1988 Oct 1
Externally publishedYes

ASJC Scopus subject areas

  • Organic Chemistry

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