Tunable and highly regio- and diastereoselective vinylogous Mannich-type reaction of dioxinone-derived silyl dienolate

J Org Chem. 2009 Aug 7;74(15):5754-7. doi: 10.1021/jo900977y.

Abstract

A tunable and highly regio- and diastereoselective vinylogous Mannich-type reaction of dioxinone-derived silyl dienolate (1) with chiral N-tert-butanesulfinyl imino ester (2) was developed. By appropriate choice of Lewis acid catalyst, two diastereomers of the gamma-product were obtained, respectively, with dr up to 95:5. The procedure for the Ag(I)-catalyzed vinylogous Mannich-type reaction also provided facile access to the alpha-regioisomer with excellent diastereoselectivities (up to >99:1 dr) by changing the counterion of the Ag(I) salt.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Acids / chemistry
  • Catalysis
  • Dioxanes / chemistry*
  • Esters / chemical synthesis*
  • Esters / chemistry*
  • Molecular Structure
  • Silver / chemistry
  • Stereoisomerism

Substances

  • Acids
  • Dioxanes
  • Esters
  • Silver