Palladium-Catalyzed Asymmetric Tandem Denitrogenative Heck/Tsuji-Trost of Benzotriazoles with 1,3-Dienes

The asymmetric denitrogenative cycloaddition has emerged as a powerful tool to build chiral aza-heterocyles. However, only one example of asymmetric denitrogenative cycloaddition of benzotriazole with unsaturated hydrocarbons has been explored so far, because the ring-opening of benzotriazole to generate a-imino metal carbenoid species is a thermodynamically unfavorable process. We herein report an efficient asymmetric denitrogenative cycloaddition of benzotriazoles with cyclic and acyclic 1,3-dienes enabled by Pd and chiral sulfonamide phosphine ligand. A variety of substituted hexahydrocarbazoles and indolines were delivered in good yields with high ee values. Interestingly, a pair of enantiomers could be obtained with the use of Xu1 and PC2 with the same absolute configuration. The synthetic utilities of the optically active hexahydrocarbazoles were also showcased.

Automated summary

An efficient asymmetric denitrogenative cycloaddition of benzotriazoles with cyclic and acyclic 1,3-dienes was reported, delivering a variety of substituted hexahydrocarbazoles and indolines in good yields with high enantiomeric excess values. Interestingly, a pair of enantiomers with the same absolute configuration could be obtained using different chiral ligands. The synthetic utilities of the optically active hexahydrocarbazoles were also demonstrated.