Dual Rh(II)/Pd(0) Relay Catalysis Involving Sigmatropic Rearrangement Using N‑Sulfonyl Triazoles and 2‑Hydroxymethylallyl Carbonates

Dual Rh(II)/Pd(0) relay catalysis of N-sulfonyl triazoles and 2-hydroxymethylallyl carbonates has been developed, which affords N-sulfonyl pyrrolidines in moderate to good yields with high diastereoselectivities. The reaction proceeds via a relay mechanism involving O–H insertion onto the α-imino Rh(II)–carbene, [3,3]-sigmatropic rearrangement, dipole formation through Pd(0)-catalyzed decarboxylation, and intramolecular N-allylation, leading to the formation of multiple bonds in a one-pot operation.