Kinetic and Dynamic Kinetic Resolution of Racemic Tertiary Bromides by Pentanidium‐Catalyzed Phase‐Transfer Azidation.

Ren, Jingyun; Ban, Xu; Zhang, Xin; Tan, Siu Min; Lee, Richmond; Tan, Choon‐Hong

We have developed a method to afford enantiomerically enriched tertiary azides and bromides through pentanidium‐catalyzed kinetic resolution (KR) of racemic tertiary bromides under base‐free conditions. We found that the absence of water is crucial to attain a high selectivity factor (s). On the other hand, new experimental observations and DFT modeling led us to propose that enantioconvergent azidation of tertiary bromides proceeded through dynamic kinetic resolution (DKR). The investigations particularly identified the crucial roles of base and water in the enantioconvergent process, thus supporting the proposal that the tertiary bromide isomerizes in the presence of base and water through a SN2X pathway.

KINETIC resolution; AZIDATION; BROMIDES; AZIDES

Angewandte Chemie, 2020, Vol 132, Issue 23, p9140

0044-8249

Academic Journal

10.1002/ange.202000138