Enantioselective Nitrene Transfer to Hydrocinnamyl Alcohols and Allylic Alcohols Enabled by Systematic Exploration of the Structure of Ion-Paired Rhodium Catalysts.

ABSTRACT: This work describes highly enantioselective nitrene transfer to hydrocinnamyl alcohols (benzylic C-H amination) and allylic alcohols (aziridination) using ion-paired Rh (II,II) complexes based on anionic variants of Du Bois' esp ligand that are associated with cinchona alkaloid-derived chiral cations. Directed by a substrate hydroxyl group, our previous work with these complexes had not been able to achieve high enantioselectivity on these most useful short-chain compounds, and we overcame this challenge through a combination of catalyst design and modified conditions. A hypothesis that modulation of the linker between the anionic sulfonate group and the central arene spacer might provide a better fit for shorter chain length substrates led to the development of a new biaryl-containing sca

SUBMITTER: Hodson NJ 

PROVIDER: S-EPMC11328136 | biostudies-literature | 2024 Aug

REPOSITORIES: biostudies-literature