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

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 alpha to oxygen. The dirhodium catalyst Rh-2(S-NTTL)(4) is the most effective chiral catalyst for triazole-derived carbene transformations, whereas Rh-2(S-TPPTTL)(4) works best for carbenes derived from aryldiazoacetates. The reactions afford a variety of delta-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.