Rh-catalyzed [4 + 2] carbocyclization of vinylarylaldehydes with alkenes and alkynes leading to substituted tetralones and 1-naphthols.

Regio-, diastereo-, and enantioselective intermolecular [4 + 2] carbocyclizations of vinylarylaldehydes with alkenes and alkynes leading to substituted tetralones and 1-naphthols have been developed by using a cationic rhodium(I)/dppb or dppp complex as a catalyst.

Cationic rhodium(I)/BINAP complex-catalyzed isomerization of secondary propargylic alcohols to alpha,beta-enones.

We have developed a cationic rhodium(I)/BINAP complex-catalyzed isomerization of secondary propargylic alcohols to alpha,beta-enones. The asymmetric variant of this reaction, a kinetic resolution of secondary propargylic alcohols, was also developed with good selectivity. The mechanistic study revealed that the isomerization proceeds through intramolecular 1,3- and 1,2-hydrogen migration pathways. [reaction: see text]