Photocatalytic Selective 1,2‐Thiocyanato‐Imination of Alkenes

Abstract A photoinduced energy transfer strategy has been developed for the direct 1,2‐thiocyanato‐imination of alkenes using N ‐SCN reagents. The methodology facilitates the synthesis of β ‐aminothiocyanates through N−S bond cleavage, with over 30 examples exhibiting yields up to 88%. Mechanistic studies reveal a radical pathway involving the generation of thiocyanate and iminyl radical species. The resulting β ‐aminothiocyanate serves as valuable building blocks for diverse transformations, particularly in the construction of SCN‐containing bioactive molecules with potential pharmaceutical applications.