Mechanism and origin of stereoselectivity in Lewis acid catalyzed [2 + 2] cycloadditions of ketenes with aldehydes Academic Article uri icon


  • Divergent rate-limiting steps for the formation of diastereomeric products! Evidence for this unexpected finding comes from experimental and theoretical studies of the title reaction. The predicted differing rate-determining steps (rds) in the formation of cis- and trans--lactones (see scheme; cy = cyclohexyl, TBS = tert-butyldimethylsilyl) are used to explain the stereoselectivity of these reactions and suggest that a broader range of mechanistic possibilities should sometimes be considered in reactions leading to diastereomeric products.

published proceedings

  • Angewandte Chemie - International Edition

author list (cited authors)

  • Singleton, D. A., Wang, Y., Yang, H. W., & Romo, D.

citation count

  • 41

publication date

  • January 2002