Delayed catalyst function enables direct enantioselective conversion of nitriles to NH₂-amines.

ABSTRACT: Accessing enantiomerically enriched amines often demands oxidation-state adjustments, protection and deprotection processes, and purification procedures that increase cost and waste, limiting applicability. When diastereomers can be formed, one isomer is attainable. Here, we show that nitriles, largely viewed as insufficiently reactive, can be transformed directly to multifunctional unprotected homoallylic amines by enantioselective addition of a carbon-based nucleophile and diastereodivergent reduction of the resulting ketimine. Successful implementation requires that competing copper-based catalysts be present simultaneously and that the slower-forming and less reactive one engages first. This challenge was addressed by incorporation of a nonproductive side cycle, fueled selectively by i

SUBMITTER: Zhang S 

PROVIDER: S-EPMC6921520 | biostudies-literature | 2019 Apr

REPOSITORIES: biostudies-literature