Cobalt-electrocatalytic HAT for functionalization of unsaturated C-C bonds.
Cobalt-electrocatalytic HAT for functionalization of unsaturated C-C bonds.
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DOI：
10.1038/s41586-022-04595-3
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发表时间：
2022-05
期刊：
影响因子：
64.8
通讯作者：
中科院分区：
文献类型：
--
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过渡金属氢化物（TMH）的研究和应用是20世纪60年代初以来化学研究的一个活跃领域，已广泛分为通过质子还原产生氢来储存能量和在有机合成中官能化不饱和C-C、C-O和C-N键的领域。在前一种情况下，自20世纪50年代以来，用于驱动这种反应性的电化学手段已经司空见惯，但是在合成化学中使用化学计量的外源性有机和金属基还原剂来利用TMH的能力仍然是规范。特别地，基于Co的TMH已经发现广泛用于复杂分子构造中烯烃和炔的衍生化，通常经由净氢原子转移（HAT）。在这里，我们展示了如何在现代有机合成的背景下利用几十年的能量存储先例启发的电催化方法。该策略不仅在可持续性和效率方面提供益处，而且还能够增强化学选择性和独特且可调的反应性。因此，示例了跨越数十种底物的十种不同的反应歧管，沿着对这种可扩展的电化学进入Co-H生成的详细机理见解，其独特地通过低价中间体发生。
The study and application of transition metal hydrides (TMH), an active area of chemical research since the early 1960’s, has been broadly bifurcated into fields focused on energy storage through the reduction of protons to generate hydrogen and in organic synthesis for the functionalization of unsaturated C–C, C–O, and C–N bonds. In the former instance, electrochemical means for driving such reactivity has been commonplace since the 1950’s but the use of stoichiometric exogenous organic- and metal-based reductants to harness the power of TMHs in synthetic chemistry remains the norm. In particular, Co-based TMHs have found widespread use for the derivatization of olefins and alkynes in complex molecule construction, often via a net hydrogen atom transfer (HAT). Here, we show how an electrocatalytic approach inspired by decades of energy storage precedent can be leveraged in the context of modern organic synthesis. This strategy not only offers benefits in terms of sustainability and efficiency but also enables enhanced chemoselectivity and unique and tunable reactivity. Ten different reaction manifolds across dozens of substrates are thus exemplified, along with detailed mechanistic insight on this scalable electrochemical entry to Co-H generation that uniquely takes place through a low-valent intermediate.
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影响因子：
15
作者：
Lo JC;Kim D;Pan CM;Edwards JT;Yabe Y;Gui J;Qin T;Gutiérrez S;Giacoboni J;Smith MW;Holland PL;Baran PS
通讯作者：
Baran PS
影响因子：
3.9
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Schoenebeck, Franziska
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通讯作者：
Waymouth, Robert M.
影响因子：
5.2
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通讯作者：
Boger, Dale L.