Evidence of Boron Assistance for CO2 Activation during Copper-Catalyzed Boracarboxylation of Vinyl Arenes: A Synthetic Model for Cooperative Fixation of CO2

IF 3.8 3区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Comments on Inorganic Chemistry Pub Date : 2020-02-23 DOI:10.1080/02603594.2020.1726328

Notashia N. Baughman, Brian V. Popp

引用次数: 3

Abstract

ABSTRACT In this comment, insights gained from density functional theory into the mechanism by which the Cu(I)-catalyzed boracarboxylation of vinyl arenes occurs with specific focus on the CO2 insertion step are presented. Preliminary calculations indicated a potential non-covalent interaction between boron and CO2 in the carboxylation transition state, implicating cooperative CO2 activation. A study of boron Lewis acidity was conducted through substitution of sp2 mono-boron substituents. An inverse correlation between boron valence deficiency (BVD) and the enthalpic barrier of CO2 insertion into the β-borylbenzyl-Cu(I) bond was revealed, supporting Lewis acid/base cooperativity between boron and the proximal oxygen of CO2 at the carboxylation insertion transition state. These findings suggest that future methodology development should consider strategic incorporation of similar Lewis acidic functionality to facilitate carboxylation of challenging substrates. Graphical abstract

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铜催化乙烯基芳烃硼羧化反应过程中硼辅助CO2活化的证据:CO2协同固定的合成模型

在这篇评论中，从密度泛函理论中获得了对Cu(I)催化乙烯基芳烃硼羧化发生机理的见解，并特别关注了CO2插入步骤。初步计算表明，在羧基化过渡态，硼和CO2之间可能存在非共价相互作用，这意味着协同CO2活化。采用sp2单硼取代基对硼的路易斯酸性进行了研究。硼价缺位(BVD)与CO2插入β-硼基苄基- cu (I)键的焓势之间呈负相关，支持了在羧基化插入过渡态硼与CO2近端氧之间的Lewis酸/碱协同作用。这些发现表明，未来的方法发展应该考虑战略性地结合类似的刘易斯酸性功能，以促进具有挑战性的底物的羧基化。图形抽象

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

Comments on Inorganic Chemistry 化学-无机化学与核化学

CiteScore

9.00

自引率

1.90%

发文量

审稿时长

>12 weeks

期刊介绍： Comments on Inorganic Chemistry is intended as a vehicle for authoritatively written critical discussions of inorganic chemistry research. We publish focused articles of any length that critique or comment upon new concepts, or which introduce new interpretations or developments of long-standing concepts. “Comments” may contain critical discussions of previously published work, or original research that critiques existing concepts or introduces novel concepts. Through the medium of “comments,” the Editors encourage authors in any area of inorganic chemistry - synthesis, structure, spectroscopy, kinetics and mechanisms, theory - to write about their interests in a manner that is both personal and pedagogical. Comments is an excellent platform for younger inorganic chemists whose research is not yet widely known to describe their work, and add to the spectrum of Comments’ author profiles, which includes many well-established inorganic chemists.