人工手性三核锌催化剂:酮类不对称硼氢化反应的设计、自组装和空前效率

IF 10.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY
Jingxi He, , , Shuxin Jiang, , , Yu Qiu, , , Yingchao Liu, , , Kuiling Ding*, , and , Xiaoming Wang*, 
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引用次数: 0

摘要

开发具有与自然界酶相媲美的效率的人工催化剂是均相金属催化领域最重要但最具挑战性的目标之一。受到金属酶的优异性能的启发,通过合理设计配体,利用近端催化位点的协同作用来设计和开发高效的双/多核催化剂引起了人们的广泛关注。本文报道了手性六齿BINOL-dipyox配体与醋酸锌自组装成一个定义良好的三核锌配合物,在极低的催化剂负载(0.005 mol %)下,以前所未有的19,400的周转率(TON)在酮的对映选择性硼化反应中表现出超高的催化效率。机理研究表明,协同Lewis酸活化模式在催化过程中起作用,因此,强调了三核结构的独特优势。本文报道了一种人工手性三核锌催化剂的合理设计和自组装,该催化剂在对映选择性酮硼氢化反应中表现出优异的效率。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Artificial Chiral Trinuclear Zn Catalysts: Design, Self-Assembly and Unprecedented Efficiency in Asymmetric Hydroboration of Ketones

The development of artificial catalysts with efficiency that can rival those of Nature’s enzymes represents one of the foremost yet challenging goals in homogeneous metal catalysis. Inspired by the exceptional performance of metalloenzymes, the design and development of highly efficient bi/multinuclear catalysts via judicious ligand design, by taking advantage of the cooperative action of the proximal catalytic sites, has attracted great attention. Herein, we report the self-assembly of a chiral hexadentate BINOL-dipyox ligand with zinc acetate into a well-defined trinuclear zinc complex, which demonstrated ultrahigh catalytic productivity in the enantioselective hydroboration of ketones with an unprecedented turnover number (TON) of 19,400 at an extremely low catalyst loading (0.005 mol %). Mechanistic investigations reveal that a cooperative Lewis acid activation mode is operating in the catalytic process, hence, underscoring the unique advantages of the trinuclear architecture.

This work reports the rational design and self-assembly of an artificial chiral trinuclear zinc catalyst, which exhibits exceptional efficiency in enantioselective ketone hydroboration.

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来源期刊
ACS Central Science
ACS Central Science Chemical Engineering-General Chemical Engineering
CiteScore
25.50
自引率
0.50%
发文量
194
审稿时长
10 weeks
期刊介绍: ACS Central Science publishes significant primary reports on research in chemistry and allied fields where chemical approaches are pivotal. As the first fully open-access journal by the American Chemical Society, it covers compelling and important contributions to the broad chemistry and scientific community. "Central science," a term popularized nearly 40 years ago, emphasizes chemistry's central role in connecting physical and life sciences, and fundamental sciences with applied disciplines like medicine and engineering. The journal focuses on exceptional quality articles, addressing advances in fundamental chemistry and interdisciplinary research.
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