Regioselective Synthesis of 1,4-Dienes via Palladium-Catalyzed Oxidative Allylation of N-Tosylhydrazones

作者：Jin, Yangbin; Li, Chunsheng; Wu, Wanqing^*; Jiang, Huanfeng^*

来源：Advanced Synthesis and Catalysis, 2023, 365(14): 2338-2343.

DOI：10.1002/adsc.202300319

• allyl-Pd electrophile intermediate
• olefination
• skipped dienes

A palladium-catalyzed allylic C-H oxidative allylation of N-tosylhydrazones to synthesize skipped 1,4-dienes is demonstrated. This direct allylic alkylation reaction has excellent site selectivity, tolerates a wide range of functional groups, and affords 1,4-dienes in moderate to good yield. Moreover, this olefination method allows the regio- and stereoselective synthesis of 1,4-dienes containing a trisubstituted alkene. Preliminary mechanistic studies reveal that the reaction undergoes allylic C(sp(3))-H activation and a subsequent carbene migratory insertion.