Synthesis and Reactions of Phosphine-Boranes. Synthesis of New Bidentate Ligands with Homochiral Phosphine Centers via Optically Pure Phosphine-Boranes

Tsuneo Imamoto, Toshiyuki Oshiki, Takashi Onozawa, Tetsuo Kusumoto, Kazuhiko Sato

Research output: Contribution to journalArticle

396 Citations (Scopus)

Abstract

Secondary and tertiary phosphine-boranes were synthesized in one-pot from phosphine oxides or substituted chlorophosphines without isolation of the intermediate phosphines. Phosphine-boranes having a methyl group were metalated with iec-butyllithium. The generated carbanions reacted with alkyl halides or carbonyl compounds to yield various phosphine-borane derivatives. The carbanions underwent copper(II)-promoted oxidative coupling without impairment of the borane functionality. Secondary phosphine-boranes reacted with alkyl halides, aldehydes, or α,β-unsaturated carbonyl compounds to give phosphine-borane derivatives having a functional group. The boranato group of phosphine-boranes was removed in a stereospecific manner with retention of configuration by treatment with a large excess of amine such as morpholine. A new route to bidentate ligands with homochiral phosphine centers has been explored by utilizing these characteristic reactivities of phosphine-boranes. Thus, optically pure (S, S)-1,2-bis(o-anisylphenylphosphino)ethane, (R, R)-1,2-bis(terr-butylphenylphosphino)ethane, and (S, S)-1,4-bis(o-anisylphenylphosphino)butane have been synthesized via phosphine-boranes.

Original languageEnglish
Pages (from-to)5244-5252
Number of pages9
JournalJournal of the American Chemical Society
Volume112
Issue number13
DOIs
Publication statusPublished - Jan 1990
Externally publishedYes

ASJC Scopus subject areas

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

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