Stereoselective Synthesis of Highly Substituted Cyclohexanes by a Rhodium-Carbene Initiated Domino Sequence

A stereoselective synthesis of cyclohexanes bearing four stereocenters from vinyldiazoacetates and allyl alcohols by a rhodium-carbene initiated domino reaction is described. The reaction cascade features a tandem ylide formation/[2,3]-sigmatropic rearrangement, oxy-Cope rearrangement, and type II carbonyl ene reaction, all of which proceed with a high degree of stereocontrol. The products are routinely isolated with excellent stereocontrol (>97:3 dr, 99% ee).