Electroreductive Carbofunctionalization of Alkenes with Alkyl Bromides via a Radical-Polar Crossover Mechanism,Journal of the American Chemical Society

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Electroreductive Carbofunctionalization of Alkenes with Alkyl Bromides via a Radical-Polar Crossover Mechanism
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2020-11-24 , DOI: 10.1021/jacs.0c08532
Wen Zhang ₁ , Song Lin ₁

Affiliation

Electrochemistry grants direct access to reactive intermediates (radicals and ions) in a controlled fashion toward selective organic transformations. This feature has been demonstrated in a variety of alkene functionalization reactions, most of which proceed via an anodic oxidation pathway. In this report, we further expand the scope of electrochemistry to the reductive functionalization of alkenes. In particular, the strategic choice of reagents and reaction conditions enabled a radical-polar crossover pathway wherein two distinct electrophiles can be added across an alkene in a highly chemo- and regioselective fashion. Specifically, we used this strategy in the intermolecular carboformylation, anti-Markovnikov hydroalkylation, and carbocarboxylation of alkenes-reactions with rare precedents in the literature-by means of the electroreductive generation of alkyl radical and carbanion intermediates. These reactions employ readily available starting materials (alkyl halides, alkenes, etc.) and simple, transition-metal-free conditions and display broad substrate scope and good tolerance of functional groups. A uniform protocol can be used to achieve all three transformations by simply altering the reaction medium. This development provides a new avenue for constructing Csp3-Csp3 bonds.

中文翻译：

通过自由基-极性交叉机制用烷基溴对烯烃进行电还原碳官能化

电化学允许以受控方式直接接触反应中间体（自由基和离子），以实现选择性有机转化。这一特征已在各种烯烃官能化反应中得到证明，其中大多数反应通过阳极氧化途径进行。在本报告中，我们进一步将电化学的范围扩展到烯烃的还原官能化。特别是，试剂和反应条件的策略选择实现了自由基-极性交叉途径，其中两种不同的亲电子试剂可以以高度化学和区域选择性的方式添加到烯烃上。具体来说，我们通过电还原生成烷基自由基和负碳离子中间体，在烯烃的分子间碳甲酰化、反马尔可夫尼科夫加氢烷基化和碳羧化反应中使用了这种策略，这在文献中是罕见的先例。这些反应采用容易获得的起始原料（卤代烷、烯烃等）和简单、无过渡金属的条件，并显示出广泛的底物范围和良好的官能团耐受性。通过简单地改变反应介质，可以使用统一的方案来实现所有三种转化。这一进展为构建 Csp3-Csp3 债券提供了新途径。

更新日期：2020-11-24

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