An unusual chiral-at-metal mechanism for BINOL-metal asymmetric catalysis

IF 14.7 1区 综合性期刊 Q1 MULTIDISCIPLINARY SCIENCES
Zhenxing Li, Pengfei Chen, Zhigang Ni, Liuzhou Gao, Yue Zhao, Ranran Wang, Congqing Zhu, Guoqiang Wang, Shuhua Li
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Abstract

Chiral binaphthols (BINOL)-metal combinations serve as powerful catalysts in asymmetric synthesis. Their chiral induction mode, however, typically relies on multifarious non-covalent interactions between the substrate and the BINOL ligand. In this work, we demonstrate that the chiral-at-metal stereoinduction mode could serve as an alternative mechanism for BINOL-metal catalysis, based on mechanistic studies of BINOL-aluminum-catalyzed asymmetric hydroboration of heteroaryl ketones. Theoretical calculations reveal that an octahedral stereogenic-at-metal aluminum alkoxide species is the most stable species within the reaction system, and also is the catalytic relevant intermediate, promoting the stereo-determining hydroboration reaction through a ligand-assisted hydride transfer mechanism rather than the conventional hydroalumination mechanism. These computations reproduce the experimental selectivities and also rationalize the stereoinduction mechanism, which arises from the aluminum-centered chirality induced by chiral BINOL ligands during diastereoselective assembly. The reliability of the proposed mechanism could be verified by the single-crystal X-ray diffraction characterization of the octahedral aluminum alkoxide complex. Additional NMR and Electronic Circular Dichroism (ECD) experiments elucidated the behavior of the hexacoordinated aluminum alkoxide in the solution phase. We anticipate that these findings will extend the applicability of BINOL-metal catalysis to a broader range of reactions.

Abstract Image

双酚-金属不对称催化的不寻常手性-金属机理
手性双酚(BINOL)-金属组合在不对称合成中是一种强有力的催化剂。然而,它们的手性诱导模式通常依赖于底物与BINOL配体之间的多种非共价相互作用。在这项工作中,我们通过对binol -铝催化的杂芳酮不对称硼氢化的机理研究,证明了手性-金属立体感应模式可以作为binol -金属催化的另一种机制。理论计算表明,八面体立体金属铝烷氧化物是反应体系中最稳定的物质,也是催化的相关中间体,通过配体辅助氢化物转移机制而不是传统的氢铝化机制来促进立体硼化反应。这些计算重现了实验选择性,也合理化了立体诱导机制,这是由于手性BINOL配体在非对映选择性组装过程中引起的铝中心手性。八面体铝醇盐配合物的单晶x射线衍射表征验证了该机理的可靠性。附加的核磁共振和电子圆二色性(ECD)实验阐明了六配位醇铝在溶液中的行为。我们预计这些发现将扩大binol -金属催化的适用性,以更广泛的反应范围。
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
Nature Communications
Nature Communications Biological Science Disciplines-
CiteScore
24.90
自引率
2.40%
发文量
6928
审稿时长
3.7 months
期刊介绍: Nature Communications, an open-access journal, publishes high-quality research spanning all areas of the natural sciences. Papers featured in the journal showcase significant advances relevant to specialists in each respective field. With a 2-year impact factor of 16.6 (2022) and a median time of 8 days from submission to the first editorial decision, Nature Communications is committed to rapid dissemination of research findings. As a multidisciplinary journal, it welcomes contributions from biological, health, physical, chemical, Earth, social, mathematical, applied, and engineering sciences, aiming to highlight important breakthroughs within each domain.
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