铜催化区域选择性脱氢si - o偶联拆分无环1,3-二醇的动力学研究

IF 13.1 1区化学 Q1 CHEMISTRY, PHYSICAL

ACS Catalysis Pub Date : 2025-04-22 DOI:10.1021/acscatal.5c0154310.1021/acscatal.5c01543

Sophie C. Schulze, and , Martin Oestreich*,

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引用次数: 0

摘要

报道了硅- o与氢硅烷区域选择性偶联非酶动力学分解无环1,3-二醇的方法。以（R，R）-Ph-BPE为手性配体的原位形成的Cu-H催化剂促进了其中一个羟基的对映选择性硅基化。对映体和区域异构体的区别很大程度上取决于氢硅烷的选择，双（4-茴香基）取代叔氢硅烷的选择结果最好。广泛的抗1,3-二醇具有良好到高的选择性因子，特别是在亚甲基部分含有环丙基-1,1-二基的衍生物。

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Kinetic Resolution of Acyclic 1,3-Diols by Copper-Catalyzed Regioselective Dehydrogenative Si–O-Coupling

A nonenzymatic kinetic resolution of acyclic 1,3-diols by regioselective Si–O coupling with a hydrosilane is reported. The in situ-formed Cu–H catalyst with (R,R)-Ph-BPE as the chiral ligand facilitates the enantioselective silylation of one of the two hydroxy groups. The differentiation between both the enantiomers and the regioisomers strongly depends on the choice of the hydrosilane with a bis(4-anisyl)-substituted tertiary hydrosilane giving the best results. A broad range of anti-1,3-diols is resolved with good to high selectivity factors, especially derivatives bearing a cycloprop-1,1-diyl group at the methylene moiety.

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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.