Computational Insight into the Enantioselective Nucleophilic Borylation of a Polarized C═O Double Bond Catalyzed by Diphosphine/Borylcopper(I) Complexes

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• 作者：Koji Kubota ; Mingoo Jin ; Hajime Ito
• 刊名：Organometallics
• 出版年：2016
• 出版时间：May 23, 2016
• 年：2016
• 卷：35
• 期：10
• 页码：1376-1383
• 全文大小：625K
• 年卷期：0
• ISSN：1520-6041

文摘

Density functional theory calculations were performed to validate the proposed reaction mechanism for the enantioselective nucleophilic borylation of a polarized C═O double bond in the presence of diphosphine/borylcopper(I) complexes. Consequently, we successfully elucidated the origin for the regioselectivity and the mechanism for the enantioselectivity of the reaction. We also obtained theoretical explanations for the fact that the presence of a proton source gave a higher reactivity and a better enantioselectivity in the borylation reaction of aldehydes with a copper(I)/(R)-DTBM-SEGPHOS complex catalyst. This study is particularly valuable toward the development and design of novel enantioselective borylation reactions with polarized carbon–heteroatom double bonds.