Reversible 1,3-anti/syn-stereochemical courses in copper-catalyzed γ-selective allyl-alkyl coupling between chiral allylic phosphates and alkylboranes

Kazunori Nagao, Umi Yokobori, Yusuke Makida, Hirohisa Ohmiya, Masaya Sawamura

Research output: Contribution to journalArticle

41 Citations (Scopus)

Abstract

The stereochemical courses of the copper-catalyzed allyl-alkyl coupling between enantioenriched chiral allylic phosphates and alkylboranes were switchable between 1,3-anti and 1,3-syn selectivities by the choice of solvents and achiral alkoxide bases with different steric demands. The reactions with γ-silylated allylic phosphates allow efficient synthesis of enantioenriched chiral allylsilanes with tertiary or quaternary carbon stereogenic centers. Cyclic and acyclic bimodal participation of alkoxyborane species in an organocopper addition-elimination sequence is proposed to account for the phenomenon of the anti/syn-stereochemical reversal.

Original languageEnglish
Pages (from-to)8982-8987
Number of pages6
JournalJournal of the American Chemical Society
Volume134
Issue number21
DOIs
Publication statusPublished - May 30 2012
Externally publishedYes

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Copper
Phosphates
Carbon
allylsilane

All Science Journal Classification (ASJC) codes

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

Cite this

Reversible 1,3-anti/syn-stereochemical courses in copper-catalyzed γ-selective allyl-alkyl coupling between chiral allylic phosphates and alkylboranes. / Nagao, Kazunori; Yokobori, Umi; Makida, Yusuke; Ohmiya, Hirohisa; Sawamura, Masaya.

In: Journal of the American Chemical Society, Vol. 134, No. 21, 30.05.2012, p. 8982-8987.

Research output: Contribution to journalArticle

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