Distal Allylic/Benzylic C−H Functionalization of Silyl Ethers Using Donor/Acceptor Rhodium(II) Carbenes

Abstract

Regio- and stereoselective distal allylic/benzylic C-H functionalization of allyl and benzyl silyl ethers was achieved using rhodium(II) carbenes derived from N-sulfonyltriazoles and aryldiazoacetates as carbene precursors. The bulky rhodium carbenes led to highly site-selective functionalization of less activated allylic and benzylic C-H bonds even in the presence of electronically preferred C-H bonds located α to oxygen. The dirhodium catalyst Rh2 (S-NTTL)4 is the most effective chiral catalyst for triazole-derived carbene transformations, whereas Rh2 (S-TPPTTL)4 works best for carbenes derived from aryldiazoacetates. The reactions afford a variety of δ-functionalized allyl silyl ethers with high diastereo- and enantioselectivity. The utility of the present method was demonstrated by its application to the synthesis of a 3,4-disubstituted l-proline scaffold.