远是多远?弱非共价相互作用支配着酞菁钌与远端(R)-BINOL取代基催化的对映选择性环丙化反应

IF 6.5 1区 化学 Q2 CHEMISTRY, PHYSICAL
Alexander A. Dmitrienko , Andrey P. Kroitor , Liudmila I. Demina , Gayane A. Kirakosyan , Yulia G. Gorbunova , Aslan Yu. Tsivadze , Alexander G. Martynov , Alexander B. Sorokin
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引用次数: 0

摘要

合成了一种手性双(r -联萘氧基)桥联酞菁钌配合物,并对其在苯乙烯衍生物与重氮酯的环丙烷化反应中进行了研究。尽管酞菁配体中的不对称诱导手性取代基位于距离催化中心相当远的位置,但该配合物表现出明显的立体选择性,这取决于底物的性质。具体来说,从重氮乙酸乙酯(EDA)转变为体积较大的重氮乙酸叔丁酯(tBuDA)显著提高了苯乙烯(S,S)-环丙烷衍生物的反顺比从6:1提高到49:1,对映体过量从27 %提高到71 %。此外,使用各种取代苯乙烯可以获得极高的反式/顺式比(高达499:1)和有希望的对映体过量(高达83 %)。大多数反应是在极低的催化剂负荷0.02 mol%下进行的。详细的DFT计算研究了苯乙烯和tBuDA之间的反应,准确地再现了实验环丙烷化对映体选择性,解释了(S,S)-环丙烷衍生物的优先形成。分子中原子量子理论的非共价相互作用分析(QTAIM)和能量分解分析(ETS-NOCV)均表明,弱相互作用在稳定对映体决定过渡态中起着至关重要的作用。这项工作有力地证明,即使手性取代基远离催化中心,具有适当设计的刚性手性腔和适当的碳的催化体系也可以实现有希望的不对称诱导。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

How far is far? Weak noncovalent interactions govern enantioselective cyclopropanation catalyzed by ruthenium phthalocyanine with remote (R)-BINOL substituents

How far is far? Weak noncovalent interactions govern enantioselective cyclopropanation catalyzed by ruthenium phthalocyanine with remote (R)-BINOL substituents

How far is far? Weak noncovalent interactions govern enantioselective cyclopropanation catalyzed by ruthenium phthalocyanine with remote (R)-BINOL substituents
A chiral bis-(R-binaphthoxy)-bridged ruthenium phthalocyanine complex was synthesized and examined in the cyclopropanation of styrene derivatives with diazo esters. Despite the asymmetry-inducing chiral substituents in the phthalocyanine ligand being positioned at a considerable distance from the catalytic center, the complex exhibits significant stereoselectivity, depending on the nature of the substrates. Specifically, switching from ethyl diazoacetate (EDA) to the bulkier tert-butyl diazoacetate (tBuDA) dramatically improved the trans/cis ratio from 6:1 to 49:1 and the enantiomeric excess from 27 % to 71 % for the (S,S)-cyclopropane derivative of styrene. Furthermore, extremely high trans/cis ratios (up to 499:1) and promising enantiomeric excesses (up to 83 %) were achieved using various substituted styrenes. Most reactions were carried out with an exceptionally low catalyst loading of 0.02 mol%. A detailed DFT computational study of the reaction between styrene and tBuDA accurately reproduced the experimental cyclopropanation enantioselectivity, explaining the preferential formation of the (S,S)-cyclopropane derivative. Non-covalent interaction analysis within quantum theory of atoms in molecules (QTAIM) and energy decomposition analysis (ETS-NOCV) both revealed that weak interactions played a crucial role in stabilizing the enantio-determining transition states. This work firmly demonstrates that a catalytic system with a properly designed rigid chiral cavity combined with an appropriate carbene can achieve promising asymmetric induction, even when the chiral substituents are remote from the catalytic center.
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来源期刊
Journal of Catalysis
Journal of Catalysis 工程技术-工程:化工
CiteScore
12.30
自引率
5.50%
发文量
447
审稿时长
31 days
期刊介绍: The Journal of Catalysis publishes scholarly articles on both heterogeneous and homogeneous catalysis, covering a wide range of chemical transformations. These include various types of catalysis, such as those mediated by photons, plasmons, and electrons. The focus of the studies is to understand the relationship between catalytic function and the underlying chemical properties of surfaces and metal complexes. The articles in the journal offer innovative concepts and explore the synthesis and kinetics of inorganic solids and homogeneous complexes. Furthermore, they discuss spectroscopic techniques for characterizing catalysts, investigate the interaction of probes and reacting species with catalysts, and employ theoretical methods. The research presented in the journal should have direct relevance to the field of catalytic processes, addressing either fundamental aspects or applications of catalysis.
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