Rhodium(I)-catalyzed intramolecular carbonylative [2+2+1] cycloadditions and cycloisomerizations of bis(sulfonylallene)s

Chemistry. 2010 May 3;16(17):5173-83. doi: 10.1002/chem.200903568.

Abstract

Novel [{RhCl(CO)dppp}(2)]-catalyzed intramolecular carbonylative [2+2+1] cycloadditions of bis(phenylsulfonylallene) derivatives under CO, leading to the facile formation of bis(phenylsulfonyl)bicyclo[n.3.0] frameworks (n=4-6), have been developed. The terminal double bonds of both allenyl moieties served exclusively as the two pi-components. In particular, this newly developed method was shown to be a powerful tool for the construction of bicyclo[6.3.0]undecadienones, which have hardly been prepared by the known Pauson-Khand (-type) reactions. The bicyclo[7.3.0]dodecadienone homologue (one extra carbon) could be formed in rather low yields. Alternatively, novel cycloisomerizations of bis(phenylsulfonylallene) derivatives with catalysis by the same Rh(I) complex under N(2) readily produced the 3,4-dimethylene-2,5-bis(phenylsulfonyl)cyclononene and the corresponding cyclooctene and cycloheptene frameworks.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Alkadienes / chemical synthesis*
  • Alkadienes / chemistry
  • Catalysis
  • Combinatorial Chemistry Techniques*
  • Cyclization
  • Molecular Structure
  • Rhodium / chemistry*
  • Stereoisomerism
  • Sulfones / chemical synthesis*
  • Sulfones / chemistry

Substances

  • Alkadienes
  • Sulfones
  • propadiene
  • Rhodium