金属和酶催化碳烯插入 X-H 和 C(sp2)-H 键的机理和立体选择性。

IF 40.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Chemical Society Reviews Pub Date : 2024-10-11 DOI:10.1039/D4CS00742E
Reena Balhara, Ritwika Chatterjee and Garima Jindal
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引用次数: 0

摘要

利用 TMs(过渡金属)(Fe、Cu、Pd、Rh、Au 等)和酶催化碳烯插入 X-H/C(sp2)-H,构建高度精通的 C-X(X = O、N、S 等)和 C-C 键是一种用途广泛的策略。这主要是通过 TM 与重氮化合物的相互作用原位生成金属碳烯来实现的。在过去的几十年中,利用各种 TM 进行的 X-H 键插入反应取得了重大进展。这些反应通常采用逐步离子途径,在这种途径中,对金属碳烯的亲核攻击会导致生成金属酰化物。这种中间体标志着反应级联中的一个关键环节,为质子转移提供了多种途径,从而产生 X-H 插入产物。C(sp2)-H 插入反应的机理与 X-H 插入反应的机理十分相似,因此也包括在这里。碳烯插入反应的一大发展是使用工程酶作为催化剂。自 Arnold 于 2013 年首次报道非天然 "碳烯转移酶""P411 "以来,文献中已报道了几种基于血红素的酶,可催化 C(sp2)-H、N-H 和 S-H 键的各种生物碳烯插入反应。这些酶具有调节反应中间体的取向和构象的非凡能力,有利于立体选择性碳烯转移。然而,由于缺乏合适的立体化学模型,阻碍了采用包括酶在内的孤独手性催化剂进行不对称反应的发展。我们迫切需要研究替代机制和模型,以提高我们对这些过程中立体选择性的理解,这对推动不对称合成和生物催化领域的发展至关重要。本综述旨在详细介绍铁、铜、钯、铑、金和酶催化的不对称 X-H 和 C(sp2)-H 插入反应的机理,重点是详细的机理和立体化学模型。综述分为几个部分,重点讨论了不同 TM 和酶催化的特定 X-H/C(sp2)-H 键类型。
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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Mechanism and stereoselectivity in metal and enzyme catalyzed carbene insertion into X–H and C(sp2)–H bonds

Constructing highly proficient C–X (X = O, N, S, etc.) and C–C bonds by leveraging TMs (transition metals) (Fe, Cu, Pd, Rh, Au, etc.) and enzymes to catalyze carbene insertion into X–H/C(sp2)–H is a highly versatile strategy. This is primarily achieved through the in situ generation of metal carbenes from the interaction of TMs with diazo compounds. Over the last few decades, significant advancements have been made, encompassing a wide array of X–H bond insertions using various TMs. These reactions typically favor a stepwise ionic pathway where the nucleophilic attack on the metal carbene leads to the generation of a metal ylide species. This intermediate marks a critical juncture in the reaction cascade, presenting multiple avenues for proton transfer to yield the X–H inserted product. The mechanism of C(sp2)–H insertion reactions closely resembles those of X–H insertion reactions and thus have been included here. A major development in carbene insertion reactions has been the use of engineered enzymes as catalysts. Since the seminal report of a non-natural “carbene transferase” by Arnold in 2013, “P411”, several heme-based enzymes have been reported in the literature to catalyze various abiological carbene insertion reactions into C(sp2)–H, N–H and S–H bonds. These enzymes possess an extraordinary ability to regulate the orientation and conformations of reactive intermediates, facilitating stereoselective carbene transfers. However, the absence of a suitable stereochemical model has impeded the development of asymmetric reactions employing a lone chiral catalyst, including enzymes. There is a pressing need to investigate alternative mechanisms and models to enhance our comprehension of stereoselectivity in these processes, which will be crucial for advancing the fields of asymmetric synthesis and biocatalysis. The current review aims to provide details on the mechanistic aspects of the asymmetric X–H and C(sp2)–H insertion reactions catalyzed by Fe, Cu, Pd, Rh, Au, and enzymes, focusing on the detailed mechanism and stereochemical model. The review is divided into sections focusing on a specific X–H/C(sp2)–H bond type catalyzed by different TMs and enzymes.

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来源期刊
Chemical Society Reviews
Chemical Society Reviews 化学-化学综合
CiteScore
80.80
自引率
1.10%
发文量
345
审稿时长
6.0 months
期刊介绍: Chemical Society Reviews is published by: Royal Society of Chemistry. Focus: Review articles on topics of current interest in chemistry; Predecessors: Quarterly Reviews, Chemical Society (1947–1971); Current title: Since 1971; Impact factor: 60.615 (2021); Themed issues: Occasional themed issues on new and emerging areas of research in the chemical sciences
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