Photocatalytic Selective 1,2‐Thiocyanato‐Imination of Alkenes

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.