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Walking metals: catalytic difunctionalization of alkenes at nonclassical sites
Chemical Science ( IF 7.6 ) Pub Date : 2020-09-07 , DOI: 10.1039/d0sc03634j Roshan K Dhungana 1 , Rishi R Sapkota 1 , Doleshwar Niroula 1 , Ramesh Giri 1
Chemical Science ( IF 7.6 ) Pub Date : 2020-09-07 , DOI: 10.1039/d0sc03634j Roshan K Dhungana 1 , Rishi R Sapkota 1 , Doleshwar Niroula 1 , Ramesh Giri 1
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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.
中文翻译：
行走金属：烯烃在非经典位点的催化双官能化
金属沿碳链的迁移是由两个最常见的有机金属基本步骤触发的：β-氢化物 (β-H) 消除和烯烃加氢金属化。这一过程预示着在碳位点上创建键的新未来，这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 消除来促进本质上注定要发生的烯烃双官能化反应的机会。扰乱。自其诞生以来近四十年，通过金属迁移进行烯烃双官能化的早期探索是零星的，其后来的发展主要由于阻止邻位烯烃双官能化的β-H消除的原始动力而中断。随着最近烯烃双官能化的激增，人们的努力已逐渐转向利用β-H消除过程在经典邻位碳以外的位点对烯烃进行双官能化，为教学简单起见，今后将其称为非经典反应位点。在这篇评论文章中，我们解救并研究了多年来此类反应的起源和发展。本综述涵盖了烯烃在孪位 (1,1)、烯丙基 (1,3) 和远程 (1, n ) 碳位点与各种偶联伙伴的双官能化反应。这些反应使得复杂分子框架的工程化成为可能，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 债券。研究人员提出的机械假设和实验证据也提出了这些独特转变的发展。从最近出现的大量报告来看，现在非常明显的是，通过金属迁移进行烯烃双官能化领域已经开始获得动力，这具有发展成为具有巨大潜力的合成方法的良好前景。
更新日期：2020-09-23
中文翻译：
行走金属：烯烃在非经典位点的催化双官能化
金属沿碳链的迁移是由两个最常见的有机金属基本步骤触发的：β-氢化物 (β-H) 消除和烯烃加氢金属化。这一过程预示着在碳位点上创建键的新未来，这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 消除来促进本质上注定要发生的烯烃双官能化反应的机会。扰乱。自其诞生以来近四十年，通过金属迁移进行烯烃双官能化的早期探索是零星的，其后来的发展主要由于阻止邻位烯烃双官能化的β-H消除的原始动力而中断。随着最近烯烃双官能化的激增，人们的努力已逐渐转向利用β-H消除过程在经典邻位碳以外的位点对烯烃进行双官能化，为教学简单起见，今后将其称为非经典反应位点。在这篇评论文章中，我们解救并研究了多年来此类反应的起源和发展。本综述涵盖了烯烃在孪位 (1,1)、烯丙基 (1,3) 和远程 (1, n ) 碳位点与各种偶联伙伴的双官能化反应。这些反应使得复杂分子框架的工程化成为可能，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 债券。研究人员提出的机械假设和实验证据也提出了这些独特转变的发展。从最近出现的大量报告来看，现在非常明显的是，通过金属迁移进行烯烃双官能化领域已经开始获得动力，这具有发展成为具有巨大潜力的合成方法的良好前景。
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