Nickel-Catalyzed Chemoselective Carbomagnesiation for Atroposelective Ring-Opening Difunctionalization

Angew Chem Int Ed Engl. 2024 Apr 23:e202401756. doi: 10.1002/anie.202401756. Online ahead of print.ABSTRACTThere is a pressing need for methods that can connect enantioenriched organic compounds with readily accessible building blocks via asymmetric functionalization of unreactive chemical bonds in organic synthesis and medicinal chemistry. Herein, the asymmetric chemoselective cleavage of two unactivated C(Ar)-O bonds in the same molecule is disclosed for the first time through an unusual nickel-catalyzed carbomagnesiation. This reaction facilitates the evolution of a novel atroposelective ring-opening difunctionalization. Utilizing readily available dibenzo bicyclic substrates, diverse valuable axially chiral biaryls are furnished with high efficiencies. Synthetic elaborations showcase the application potential of this method. The features of this method include good atom-economy, multiple roles of the nucleophile, and a simple catalytic system that enables the precise magnesiation of an α-C(Ar)-O bond and arylation of a β-C(Ar)-O bond.PMID:38651647 | DOI:10.1002/anie.202401756

Source: Angewandte Chemie - April 23, 2024 Category: Chemistry Authors: Tingting Sun Linchao Guo Qi Li Zhi-Chao Cao Source Type: research