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Copper(I)-Catalyzed Enantioconvergent Borylation of Racemic Benzyl Chlorides Enabled by Quadrant-by-Quadrant
Hiroaki Iwamoto1, Kohei Endo1, Yu Ozawa1
1Division of Applied Chemistry, Graduate School of Engineering Hokkaido University, Sapporo, Hokkaido, 060-8628, Japan.
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.
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