Modular Synthesis of Chiral 1,3-Diboronates with Differentiable Boryl Groups via Cu-Catalyzed Borylalkylation of Styrenes

IF 11.3 1区化学 Q1 CHEMISTRY, PHYSICAL

ACS Catalysis Pub Date : 2025-05-12 DOI:10.1021/acscatal.5c01288

Guoxiang Zhang, Quan-Hong Zhao, Xin-Yue Chai, Yanjie Yang, Zhuo Zhang, Kai Qu, Song Liu, Yuan Huang

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Abstract

A practical, modular approach for the preparation of enantioenriched 1,3-diboronates with differentiable boron moieties (Bdan vs Bpin) is introduced. The reaction involves borylcupration of the alkene, followed by capture of the catalytically generated alkylcopper intermediate with commercially available ICH₂Bpin to synthetically valuable 1,3-bis(boryl)alkanes. The newly developed NHC-copper catalyst is the significant parameter for the reactions, which enables to produce a wide range of chiral 1,3-diboronates in high reactivities and enantioselectivities. Furthermore, a variety of chiral building blocks could be easily accessed through chemoselective functionalization of two boron groups in a stepwise manner. The utility of this reaction was further highlighted by the efficient synthesis of the chiral precursor of Glabridin analogue. DFT calculation profiles demonstrated that after the stereoselective borylcupration, the alkylation step takes place through an S_N2-type oxidative addition mechanism of ICH₂Bpin followed by a reductive elimination.

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cu催化苯乙烯的硼基烷基化模块化合成具有可微硼基的手性1,3-二硼酸盐

介绍了一种实用的模块化方法，用于制备具有可微硼基团（Bdan vs Bpin）的富集对映体的1,3-二硼酸盐。该反应包括烯烃的硼基铜化，然后用市售的ICH2Bpin捕获催化生成的烷基铜中间体，合成有价值的1,3-二（硼基）烷烃。新开发的nhc -铜催化剂是该反应的重要参数，它能以高反应活性和对映选择性制备大范围的手性1,3-二硼酸盐。此外，通过两个硼基团的化学选择性功能化，可以很容易地逐步获得各种手性构建块。光定类似物的手性前体的高效合成进一步突出了该反应的实用性。DFT计算结果表明，在立体选择性硼基铜化后，ICH2Bpin通过sn2型氧化加成机制发生烷基化反应，随后发生还原消除反应。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

ACS Catalysis CHEMISTRY, PHYSICAL-

CiteScore

20.80

自引率

6.20%

发文量

1253

审稿时长

1.5 months

期刊介绍： ACS Catalysis is an esteemed journal that publishes original research in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. It offers broad coverage across diverse areas such as life sciences, organometallics and synthesis, photochemistry and electrochemistry, drug discovery and synthesis, materials science, environmental protection, polymer discovery and synthesis, and energy and fuels. The scope of the journal is to showcase innovative work in various aspects of catalysis. This includes new reactions and novel synthetic approaches utilizing known catalysts, the discovery or modification of new catalysts, elucidation of catalytic mechanisms through cutting-edge investigations, practical enhancements of existing processes, as well as conceptual advances in the field. Contributions to ACS Catalysis can encompass both experimental and theoretical research focused on catalytic molecules, macromolecules, and materials that exhibit catalytic turnover.