Chiral Brønsted Acid-Catalyzed Asymmetric Allyl(propargyl)boration Reaction of ortho-Alkynyl Benzaldehydes: Synthetic Applications and Factors Governing the Enantioselectivity

Elsa Rodríguez, Matthew N. Grayson, Amparo Asensio, Pablo Barrio, K. N. Houk, Santos Fustero

Research output: Contribution to journalArticlepeer-review

39 Citations (Scopus)

Abstract

Chiral Brønsted acid-catalyzed allyl(propargyl)boration of ortho-alkynyl benzaldehydes gives rise to ω-alkynyl homoallylic(homopropargylic)alcohols that can be further transformed to complex molecular scaffolds via subsequent hydroalkoxylation, ring-closing enyne metathesis (RCEYM), or intramolecular Pauson-Khand reaction (PKR). Optimizations of each two-step transformation is reported. A strong dependence between enantioselectivities and the nature of the substitution at the alkynyl moiety is observed, showcasing that the triple bond is not merely a spectator in this transformation. Density functional theory (DFT) calculations (M06-2X/6-311+G(d,p)-IEFPCM//B3LYP/6-31G(d)) show that this dependence is the result of the steric and electronic properties of the alkyne substituent.

Original languageEnglish
Pages (from-to)2506-2514
Number of pages9
JournalACS Catalysis
Volume6
Issue number4
Early online date7 Mar 2016
DOIs
Publication statusPublished - 1 Apr 2016

Keywords

  • asymmetric allylboration
  • chiral Brønsted acids
  • DFT calculations
  • diversity-oriented synthesis
  • organocatalysis

ASJC Scopus subject areas

  • Catalysis

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