Amide-directed catalytic asymmetric hydroboration of trisubstituted alkenes

Sean M. Smith, James M. Takacs

Research output: Contribution to journalArticle

71 Citations (Scopus)

Abstract

(Chemical Equation Presented) Rhodium-catalyzed hydroborations of trisubstituted alkenes are generally slow and often suffer from competing alkene isomerization. In contrast, the trisubstituted alkene moieties contained within the framework of a β,γ-unsaturated amide undergo facile reaction, perhaps facilitated by carbonyl directing effects and two-point binding of the substrate to the rhodium catalyst. Stereoisomeric substrates, for example, (E)- and (Z)-3, cleanly give rise to diastereomeric products, and thus the rhodium-catalyzed reaction is stereospecific. In addition, simple TADDOL-derived phenyl monophosphite ligands in combination with Rh(nbd)2BF 4 afford highly enantioselective catalysts (seven examples, 91-98% ee). These catalysts provide an alternative methodology to prepare Felkin or anti-Felkin acetate-aldol products and related derivatives that are obtainable from the intermediate chiral organoboranes.

Original languageEnglish (US)
Pages (from-to)1740-1741
Number of pages2
JournalJournal of the American Chemical Society
Volume132
Issue number6
DOIs
StatePublished - Mar 1 2010

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Rhodium
Alkenes
Amides
Olefins
Catalysts
Substrates
Isomerization
Acetates
Ligands
Derivatives

ASJC Scopus subject areas

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

Cite this

Amide-directed catalytic asymmetric hydroboration of trisubstituted alkenes. / Smith, Sean M.; Takacs, James M.

In: Journal of the American Chemical Society, Vol. 132, No. 6, 01.03.2010, p. 1740-1741.

Research output: Contribution to journalArticle

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