Allylic Amination of Alkenyl Alcohols: Simultaneous Control of Chemoselectivity and Enantioselectivity in Nitrene Transfer Using Ion-Paired Catalysts.

ABSTRACT: When alkene-containing substrates are functionalized using metal nitrenoid complexes, aziridination is typically the favored reaction outcome. In certain cases, careful catalyst control may permit allylic C-H amination, but enantioselective protocols are very rare. This work describes the use of ion-paired Rh paddlewheel complexes to perform enantioselective allylic amination, where the typically preferred aziridination outcome can be overcome by the directing effect operating between the catalyst and the alcohol functional group in the substrate. A survey of different functional groups reveals that in this case, alcohols provide the optimum directing effect, and we carry out a systematic study to elucidate the important features of the chiral Cinchona alkaloid-derived cation associated wi

SUBMITTER: Adams HK 

PROVIDER: S-EPMC12418313 | biostudies-literature | 2025 Sep

REPOSITORIES: biostudies-literature