Bimetallic Rhodium(II)/Indium(III) Relay Catalysis for Tandem Insertion/Asymmetric Claisen Rearrangement

The first example of catalytic insertion/asymmetric Claisen rearrangement tandem reaction of N ‐sulfonyl‐1,2,3‐triazoles with allyl alcohol esters was achieved by bimetallic relay catalytic systems involving achiral rhodium salt and chiral N , N ′‐dioxide–indium(III) complex. This manifold could overcome the limitation of single Rh II catalysis, providing a straight and facile route to various enantioenriched β/γ‐amino acid derivatives in high yields (up to 99 %) with excellent diastereo‐ and enantioselectivities (up to >95:5 dr, 98:2 er). Moreover, possible transition state models were proposed to elucidate the origin of chiral induction based on the control experiments and X‐ray crystal structure of the catalyst.