Ruthenium-Catalyzed Direct Asymmetric Reductive Amination of Diaryl and Sterically Hindered Ketones with Ammonium Salts and H2.

Ruthenium-Catalyzed Direct Asymmetric Reductive Amination of Diaryl and Sterically Hindered Ketones with Ammonium Salts and H2.
Angew Chem Int Ed Engl. 2020 Jan 17;:
Authors: Hu LA, Zhang Y, Zhang QW, Yin Q, Zhang X
Abstract
Transition metal-catalyzed direct asymmetric reductive amination (ARA) of diaryl or sterically hindered ketones remains unknown and an open challenge. Herein, Ru-catalyzed direct asymmetric reductive amination of ortho -OH-substituted diaryl and sterically hindered ketones with ammonium salts has been disclosed for the first time, offering a straightforward route toward the synthesis of synthetically useful chiral primary diarylmethylamines and sterically hindered benzylamines (up to 97% yield, 93->99% ee). The elaborations of chiral amine products into bioactive compounds have been exhibited through manipulations on the removable and convertible -OH group. Moreover, gram-scale synthesis of chiral sterically bulky amine 6ac and its application in the synthesis of a new benzo-bisoxazine ligand further showcase the utility of this method.
PMID: 31953901 [PubMed - as supplied by publisher]

Source: Angewandte Chemie - January 16, 2020 Category: Chemistry Authors: Hu LA, Zhang Y, Zhang QW, Yin Q, Zhang X Tags: Angew Chem Int Ed Engl Source Type: research