Catalytic asymmetric allylation of ketones and a tandem asymmetric allylation/diastereoselective epoxidation of cyclic enones

J Am Chem Soc. 2004 Oct 6;126(39):12580-5. doi: 10.1021/ja047758t.

Abstract

A simple procedure is reported for the catalytic asymmetric allylation of ketones, utilizing titanium tetraisopropoxide, BINOL, 2-propanol additive, and tetraallylstannane as allylating agent. A variety of ketone substrates, including acetophenone derivatives and alpha,beta-unsaturated cyclic enones, reacted to form tertiary homoallylic alcohols in good yields (67-99%) and with high levels of enantioselectivity (generally >80%). A novel one-pot enantioselective allylation/diastereoselective epoxidation has also been introduced. Thus, upon completion of the allyl addition to conjugated cyclic enones, 1 equiv of tert-butyl hydroperoxide is added and the directed epoxidation of the allylic double bond ensues to afford the epoxy alcohol with high diastereoselectivity.

Publication types

  • Research Support, U.S. Gov't, P.H.S.

MeSH terms

  • Alcohols / chemical synthesis*
  • Alcohols / chemistry
  • Allyl Compounds / chemical synthesis
  • Allyl Compounds / chemistry*
  • Catalysis
  • Epoxy Compounds / chemical synthesis*
  • Epoxy Compounds / chemistry
  • Ketones / chemical synthesis
  • Ketones / chemistry*
  • Oxidation-Reduction
  • Stereoisomerism

Substances

  • Alcohols
  • Allyl Compounds
  • Epoxy Compounds
  • Ketones