Synfacts 2009(4): 0421-0421  
DOI: 10.1055/s-0028-1087866
Metal-Catalyzed Asymmetric Synthesis and Stereoselective Reactions
© Georg Thieme Verlag Stuttgart ˙ New York

Regiodivergent Resolution of Unsymmetrical Oxabicyclic Alkenes

Contributor(s): Hisashi Yamamoto, Joshua N. Payette
R. Webster, C. Böing, M. Lautens*
University of Toronto, Canada
Further Information

Publication History

Publication Date:
23 March 2009 (online)


The Lautens group reports a rare example of a regiodivergent resolution of bridgehead-substituted oxabenzonorbornene derivatives under rhodium catalysis. From earlier work, these oxabicycles were shown to undergo [Rh(CO)2Cl]2-catalyzed addition of methanol to provide product type A based on complete substrate control. However, when these substrates were treated with a chiral rhodium complex, two regioisomers (type A and B) resulting from Rh insertion into either C-O bond were obtained each in excellent enantioselectivity. Subsequently, various oxabi­cycles and alcohol- and amine-based nucleophiles could be used under these reaction conditions.