Rhodium-catalyzed [(3+2)+2] carbocyclization of alkynylidenecyclopropanes with substituted allenes: stereoselective construction of tri- and tetrasubstituted exocyclic olefins

Abstract

The development of the stereoselective rhodium-catalyzed [(3+2)+2] carbocyclization of alkynylidenecyclopropanes (ACPs) with substituted allenes is described. This work demonstrates that activated and unactivated allenes preferentially undergo carbometalation at the distal terminus to generate tri- and tetrasubstituted exocyclic olefins with a neutral rhodium catalyst. In addition, this method provides a strategy for the total synthesis of the guaiane family of sesquiterpenes, which are not directly accessible using alkynes as exogenous π-components. Finally, the preparation of the bicyclo[5.4.0]undecane ring system using a homologated ACP tether serves to further illustrate the versatility of this approach.

Keywords: allenes; cyclizations; olefins; rhodium; synthetic methods.