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

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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 sec-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(tert-butylphenyl-phosphino)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
Publication statusPublished - Jun 20 1990
Externally publishedYes

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phosphine
Boranes
Carbonyl compounds
Ethane
Ligands
Derivatives
Butane
Aldehydes
Functional groups
Amines
Copper
Oxides
Oxidative Coupling
Phosphines

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Synthesis and reactions of phosphine-boranes. Synthesis of new bidentate ligands with homochiral phosphine centers via optically pure phosphine-boranes. / Imamoto, Tsuneo; Oshiki, Toshiyuki; Onozawa, Takashi; Kusumoto, Tetsuo; Sato, Kazuhiko.

In: Journal of the American Chemical Society, Vol. 112, No. 13, 20.06.1990, p. 5244-5252.

Research output: Contribution to journalArticle

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