Organocatalytic Asymmetric N -Allylation of N -Acyl Sulfenamides with Morita–Baylis–Hillman Carbonates

Abstract N-Acyl sulfenamides are ambident nucleophiles that typically react at sulfur, making asymmetric N-functionalization challenging. Here, we report the direct asymmetric N-allylation of N-acyl sulfenamides with MBH carbonates under transition-metal-free organocatalysis. The dimeric cinchona alkaloid (DHQD)2AQN promotes selective N-allylation with retention of the S–N bond, affording centrally chiral allylic sulfenamides in up to 93% yield and 95% ee. The reaction is scalable and the products undergo further desulfurization, cyclization, and oxidation.