Copper(I)‐Catalyzed Enantioconvergent Borylation of Racemic Benzyl Chlorides Enabled by Quadrant‐by‐Quadrant Structure Modification of Chiral Bisphosphine Ligands
- 5 June 2019
- journal article
- research article
- Published by Wiley in Angewandte Chemie International Edition
- Vol. 58 (32) , 11112-11117
Abstract
The first copper(I)‐catalyzed enantioselective borylation of racemic benzyl chlorides has been realized by a quadrant‐by‐quadrant structure modulation of QuinoxP*‐type bisphosphine ligands. This reaction converts racemic mixtures of secondary benzyl chlorides into the corresponding chiral benzylboronates with high enantioselectivity (up to 92 % ee). The results of mechanistic studies suggest the formation of a benzylic radical intermediate. The results of DFT calculations indicate that the optimal bisphosphine‐copper(I) catalyst engages in noncovalent interactions that efficiently recognize the radical intermediate, and leads to high levels of enantioselectivity.Keywords
Funding Information
- JSPS KAKENHI (17H06370, 18H03907, 16J0141006)
This publication has 47 references indexed in Scilit:
- NCIPLOT: A Program for Plotting Noncovalent Interaction RegionsJournal of Chemical Theory and Computation, 2011
- Direct enantio-convergent transformation of racemic substrates without racemization or symmetrizationNature Chemistry, 2010
- Revealing Noncovalent InteractionsJournal of the American Chemical Society, 2010
- Catalytic Asymmetric Synthesis of Chiral Tertiary Organoboronic Esters through Conjugate Boration of β-Substituted Cyclic EnonesJournal of the American Chemical Society, 2009
- Dynamic kinetic asymmetric transformation in copper catalyzed allylic alkylationChemical Communications, 2009
- Efficient Boron−Copper Additions to Aryl-Substituted Alkenes Promoted by NHC−Based Catalysts. Enantioselective Cu-Catalyzed Hydroboration ReactionsJournal of the American Chemical Society, 2009
- Synthesis of Optically Active Boron–Silicon Bifunctional Cyclopropane Derivatives through Enantioselective Copper(I)‐Catalyzed Reaction of Allylic Carbonates with a Diboron DerivativeAngewandte Chemie International Edition, 2008
- Synthesis of Optically Active Boron–Silicon Bifunctional Cyclopropane Derivatives through Enantioselective Copper(I)‐Catalyzed Reaction of Allylic Carbonates with a Diboron DerivativeAngewandte Chemie, 2008
- Catalytic Asymmetric Boration of Acyclic α,β‐Unsaturated Esters and NitrilesAngewandte Chemie, 2007
- Catalytic Asymmetric Boration of Acyclic α,β‐Unsaturated Esters and NitrilesAngewandte Chemie International Edition, 2007