Photocatalytic Activation of Less Reactive Bonds and Their Functionalization via Hydrogen-Evolution Cross-Couplings,Accounts of Chemical Research

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Photocatalytic Activation of Less Reactive Bonds and Their Functionalization via Hydrogen-Evolution Cross-Couplings
Accounts of Chemical Research ( IF 16.4 ) Pub Date : 2018-10-03 00:00:00 , DOI: 10.1021/acs.accounts.8b00267
Bin Chen ₁ , Li-Zhu Wu ₁ , Chen-Ho Tung ₁

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Cross-coupling reactions have been established as potential tools for manufacture of complex molecular frameworks of diversified interests by connecting two simple molecules through the formation of a carbon–carbon (C–C) or a carbon–heteroatom (C–X) bond. Conventional cross-couplings are transition metal-catalyzed reactions between electrophiles and nucleophiles. Generally, the electrophilic partner is an aryl or alkenyl halide, the nucleophile is an organometallic reagent, and both are obtained from prefunctionalization of their corresponding hydrocarbons. During the past decade, transition metal-catalyzed dehydrogenative cross-couplings between two carbon–hydrogen (C–H) bonds and between one C–H bond and one heteroatom–hydrogen (X–H) bond, which build a C–C and a C–X linkage respectively, have emerged as an attractive strategy in synthetic chemistry. Such straightforward couplings allow use of less functionalized reagents, thus reducing the number of steps to the target molecule and minimizing waste production. However, such reactions involve the use of stoichiometric amounts of sacrificial oxidants such as peroxides, high-valent metals, and iodine(III) oxidants. This leads to low atom economy and possible generation of toxic wastes.

中文翻译：

反应性较低的键的光催化活化及其通过氢演化交叉偶联的功能化。

通过形成碳-碳（CC）或碳-杂原子（C-X）键连接两个简单分子，交叉偶联反应已成为制造具有多元化兴趣的复杂分子框架的潜在工具。常规的交叉偶联是亲电试剂和亲核试剂之间的过渡金属催化反应。通常，亲电子伴侣是芳基或烯基卤，亲核试剂是有机金属试剂，并且两者均由其相应烃的预官能化获得。在过去的十年中，过渡金属催化的脱氢反应出现了两个碳-氢（C-H）键之间，一个C-H键与一个杂原子-氢（X-H）键之间的交叉偶联，分别建立了CC和C-X键。合成化学中一种有吸引力的策略。这种直接的偶联允许使用功能性较低的试剂，从而减少了目标分子的步骤数量，并最大程度地减少了废物产生。但是，这种反应涉及使用化学计量的牺牲氧化剂，例如过氧化物，高价金属和碘（III）氧化剂。这导致低原子经济性并可能产生有毒废物。

更新日期：2018-10-03

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