Facile Access to Cyclopropylboronates via Stereospecific Deborylative Cyclization: A Leaving Group-Assisted Activation of Geminal Diborons
Xin-Yi Chen
Shanghai Engineering Research Center of Molecular Therapeutics and New Drug Development, School of Chemistry and Molecular Engineering, East China Normal University, 3663 N Zhongshan Road, Shanghai, 200062 China
These authors contributed equally to this work.
Search for more papers by this authorFeng-Chen Gao
Shanghai Engineering Research Center of Molecular Therapeutics and New Drug Development, School of Chemistry and Molecular Engineering, East China Normal University, 3663 N Zhongshan Road, Shanghai, 200062 China
These authors contributed equally to this work.
Search for more papers by this authorPeng-Fei Ning
Shanghai Engineering Research Center of Molecular Therapeutics and New Drug Development, School of Chemistry and Molecular Engineering, East China Normal University, 3663 N Zhongshan Road, Shanghai, 200062 China
Search for more papers by this authorYi Wei
Shanghai Engineering Research Center of Molecular Therapeutics and New Drug Development, School of Chemistry and Molecular Engineering, East China Normal University, 3663 N Zhongshan Road, Shanghai, 200062 China
Search for more papers by this authorCorresponding Author
Prof. Dr. Kai Hong
Shanghai Engineering Research Center of Molecular Therapeutics and New Drug Development, School of Chemistry and Molecular Engineering, East China Normal University, 3663 N Zhongshan Road, Shanghai, 200062 China
Shanghai Frontiers Science Center of Molecule Intelligent Syntheses, School of Chemistry and Molecular Engineering, East China Normal University, 3663 N Zhongshan Road, Shanghai, 200062 China
Search for more papers by this authorXin-Yi Chen
Shanghai Engineering Research Center of Molecular Therapeutics and New Drug Development, School of Chemistry and Molecular Engineering, East China Normal University, 3663 N Zhongshan Road, Shanghai, 200062 China
These authors contributed equally to this work.
Search for more papers by this authorFeng-Chen Gao
Shanghai Engineering Research Center of Molecular Therapeutics and New Drug Development, School of Chemistry and Molecular Engineering, East China Normal University, 3663 N Zhongshan Road, Shanghai, 200062 China
These authors contributed equally to this work.
Search for more papers by this authorPeng-Fei Ning
Shanghai Engineering Research Center of Molecular Therapeutics and New Drug Development, School of Chemistry and Molecular Engineering, East China Normal University, 3663 N Zhongshan Road, Shanghai, 200062 China
Search for more papers by this authorYi Wei
Shanghai Engineering Research Center of Molecular Therapeutics and New Drug Development, School of Chemistry and Molecular Engineering, East China Normal University, 3663 N Zhongshan Road, Shanghai, 200062 China
Search for more papers by this authorCorresponding Author
Prof. Dr. Kai Hong
Shanghai Engineering Research Center of Molecular Therapeutics and New Drug Development, School of Chemistry and Molecular Engineering, East China Normal University, 3663 N Zhongshan Road, Shanghai, 200062 China
Shanghai Frontiers Science Center of Molecule Intelligent Syntheses, School of Chemistry and Molecular Engineering, East China Normal University, 3663 N Zhongshan Road, Shanghai, 200062 China
Search for more papers by this authorGraphical Abstract
A transition metal-free deborylative cyclization strategy led to the efficient synthesis of racemic and enantioenriched cyclopropylboronates. The cyclization of geminal-bis(boronates) bearing a leaving group was highly diastereoselective and stereospecific, tolerating various functional groups and heterocycles. Mechanistic studies indicated that the leaving group at the γ-position significantly promoted the activation of the gem-diboron moiety.
Abstract
Herein we reported a transition metal-free deborylative cyclization strategy, based on which two routes have been developed, generating racemic and enantioenriched cyclopropylboronates. The cyclization of geminal-bis(boronates) bearing a leaving group was highly diastereoselective, tolerating a few functional groups and applicable to heterocycles. When optically active epoxides were used as the starting materials, enantioenriched cyclopropylboronates could be efficiently prepared with >99 % stereospecificity. Mechanistic studies showed that the leaving group at the γ-position played a crucial role and significantly promoted the activation of the gem-diboron moiety.
Conflict of interest
The authors declare no conflict of interest.
Open Research
Data Availability Statement
The data that support the findings of this study are available in the supplementary material of this article.
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