Catalytic asymmetric synthesis of the endo-6-aryl-8-oxabicyclo[3.2.1]oct-3-en-2-one natural product from Ligusticum chuanxing via 1,3-dipolar cycloaddition of a formyl-derived carbonyl ylide using Rh2(S-TCPTTL)4

J Org Chem. 2010 Sep 3;75(17):6039-42. doi: 10.1021/jo101175b.

Abstract

The reaction of a six-membered cyclic formyl-carbonyl ylide derived from alpha-diazo-beta-ketoester with phenylacetylene derivatives under the catalysis of dirhodium(II) tetrakis[N-tetrachlorophthaloyl-(S)-tert-leucinate], Rh(2)(S-TCPTTL)(4), provides cycloadducts containing an 8-oxabicyclo[3.2.1]octane ring system in up to 97% ee. This represents the first example of an enantioselective 1,3-dipolar cycloaddition of a cyclic formyl-carbonyl ylide. Using this catalytic process, an asymmetric synthesis of endo-6-aryl-8-oxabicyclo[3.2.1]oct-3-en-2-one natural product 1 from Ligusticum chuanxing Hort. has been achieved.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Biological Factors / chemical synthesis*
  • Biological Factors / chemistry
  • Bridged Bicyclo Compounds / chemistry*
  • Catalysis
  • Cyclization
  • Ketones / chemistry*
  • Ligusticum / chemistry*
  • Molecular Structure
  • Organometallic Compounds / chemistry*
  • Rhodium / chemistry*
  • Stereoisomerism

Substances

  • Biological Factors
  • Bridged Bicyclo Compounds
  • Ketones
  • Organometallic Compounds
  • Rhodium