Walking metals: catalytic difunctionalization of alkenes at nonclassical sites.
Walking metals: catalytic difunctionalization of alkenes at nonclassical sites.
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DOI：
10.1039/d0sc03634j
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发表时间：
2020-09-07
期刊：
影响因子：
8.4
通讯作者：
Giri R
中科院分区：
文献类型：
--
作者：
Dhungana RK;Sapkota RR;Niroula D;Giri R
金属沿着碳链的迁移是由两个最常见的有机金属基本步骤-- β-氢化物（β-H）消除和烯烃氢金属化引发的。这一过程预示着在碳位点上产生键的新未来，这些键超出了反应性和键形成的传统智慧的原则，并提供了利用β-H消除来推进烯烃双官能化反应的机会，这是内在注定要破坏的。自其诞生近40年以来，通过金属迁移进行烯烃双官能化的早期冒险是零星的，并且其后期发展经历了一个中断，主要是由于阻止邻位烯烃双官能化的β-H消除的原始动力。随着最近烯烃双官能化的激增，努力已经逐渐转移到利用β-H消除的过程来在除了经典的邻位碳之外的位点上双官能化烯烃，为了教学的简单性，此后称为非经典反应位点。在这篇综述文章中，我们将对这些反应的起源和多年来的发展进行分析和研究。本文综述了在偕位（1，1）、烯丙基位（1，3）和远位（1，n）碳原子上的烯烃与多种偶联配体的双官能化反应。这些反应使得能够通过产生新的碳-碳（C-C）/C-C、C-C/C-杂原子（卤素、O、N、B）和C-B/C-B键来工程化复杂的分子框架。这些独特的转变的发展也与研究人员提出的机制假说和实验证据。从近年来的报道来看，金属迁移催化烯烃双官能化反应的发展势头良好，具有广阔的前景，是一种极具潜力的合成方法。烯烃可以通过β-氢化物消除和氢化金属化步骤在非常规碳位点上通过过渡金属的迁移而双官能化。
Migration of metals along a carbon chain is triggered by two of the most common organometallic elementary steps – β-hydride (β-H) elimination and alkene hydrometallation. This process heralds a new future for creating bonds at carbon sites that fall outside the tenets of the conventional wisdom for reactivity and bond formation, and provides an opportunity to leverage β-H elimination to advance the very reaction of alkene difunctionalization it is intrinsically predestined to disrupt. Almost four decades since its genesis, the early adventure for alkene difunctionalization by metal migration was sporadic, and its later development went on a hiatus primarily due to original impetus on arresting β-H elimination for vicinal alkene difunctionalization. With the recent surge on alkene difunctionalization, efforts have been gradually shifting to harnessing the process of β-H elimination to difunctionalize alkenes at sites other than the classical vicinal carbons, termed henceforth nonclassical reaction sites for pedagogical simplicity. In this review article, we extricate and examine the origin and the development of such reactions over the years. This review covers a wide range of reactions for the difunctionalization of alkenes at geminal (1,1), allylic (1,3) and remote (1,n) carbon sites with a variety of coupling partners. These reactions have enabled engineering of complex molecular frameworks with the generation of new carbon–carbon (C–C)/C–C, C–C/C–heteroatom (halogens, O, N, B) and C–B/C–B bonds. The development of these unique transformations is also presented with mechanistic hypotheses and experimental evidences put forward by researchers. Judged by the number of reports emerging recently, it is now strikingly evident that the field of alkene difunctionalization by metal migration has begun to gain momentum, which holds a great future prospect to develop into a synthetic method of enormous potential. Alkenes can be difunctionalized at unconventional carbon sites by the migration of transition metals through β-hydride elimination and hydrometallation steps.
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