Ni(II)-catalyzed asymmetric alkenylation and arylation of aryl ketones with organoborons via 1,5-metalate shift.

Autor: Wei H; Shanghai Key Laboratory of Molecular Engineering of Chiral Drugs, Frontiers Science Center for Transformative Molecules, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, 200240, Shanghai, P. R. China., Luo Y; Shanghai Key Laboratory of Molecular Engineering of Chiral Drugs, Frontiers Science Center for Transformative Molecules, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, 200240, Shanghai, P. R. China., Ren J; Shanghai Key Laboratory of Molecular Engineering of Chiral Drugs, Frontiers Science Center for Transformative Molecules, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, 200240, Shanghai, P. R. China., Yuan Q; Shanghai Key Laboratory of Molecular Engineering of Chiral Drugs, Frontiers Science Center for Transformative Molecules, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, 200240, Shanghai, P. R. China. yuanqianjia@sjtu.edu.cn., Zhang W; Shanghai Key Laboratory of Molecular Engineering of Chiral Drugs, Frontiers Science Center for Transformative Molecules, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, 200240, Shanghai, P. R. China. wanbin@sjtu.edu.cn.
Jazyk: angličtina
Zdroj: Nature communications [Nat Commun] 2024 Oct 10; Vol. 15 (1), pp. 8775. Date of Electronic Publication: 2024 Oct 10.
DOI: 10.1038/s41467-024-53005-x
Abstrakt: Chiral tertiary alcohols are an important structural motif, however, the general and efficient methodologies for their synthesis are less reported. Herein, we report a Ni(ІІ)-catalyzed asymmetric alkenylation and arylation of aryl ketones with organoborons under air via a 1,5-metalate shift strategy to obtain chiral tertiary allylic alcohols and diaryl alcohols. The reaction demonstrates good functional group tolerance and delivers chiral tertiary alcohols with good to excellent results. Furthermore, this method can be applied to the late-stage modification of drugs and the efficient synthesis of natural products. Notably, the reaction proceeds through an outer-sphere mechanism. The Ni(II) complex functions both as a Lewis acid to activate the ketone and create a chiral environment, and as coordination bridge linking the ketone and the organoboron-derived "ate" complex, facilitating the 1,5-metalate shift without forming a C-Ni bond. This approach contrasts with traditional transition metal-catalyzed nucleophilic addition reactions that involve carbon-metal bond formation.
(© 2024. The Author(s).)
Databáze: MEDLINE
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