Remote difunctionalization of unactivated alkenes is challenging but a highly attractive tactic to install two functional groups across long distances. Reported herein is the first remote difunctionalization of alkenes with CO₂. This visible‐light photoredox catalysis strategy provides a facile method to synthesize a series of carboxylic acids bearing valuable fluorine‐ or phosphorus‐containing functional groups. Moreover, this versatile protocol shows mild reaction conditions, broad substrate scope, and good functional‐group tolerance. Based on DFT calculations, a radical adds to an unactivated alkene to smoothly form a new carbon radical, followed by a 1,5‐hydrogen atom‐transfer process, the rate‐limiting step, generating a more stable benzylic radical. The reduction of the benzylic radicals by an Ir^II species generates the corresponding benzylic carbanions as the key intermediates, which further undergo nucleophilic attack with CO₂ to generate carboxylates.

中文翻译：

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可见光光氧化还原催化的未活化烯烃与二氧化碳的远程双官能化羧化反应。

未活化烯烃的远程双官能化具有挑战性，但是在长距离安装两个官能团的策略非常有吸引力。本文报道的是烯烃与CO ₂的第一个远程双官能化。这种可见光的光氧化还原催化策略提供了一种简便的方法来合成一系列带有有价值的含氟或含磷官能团的羧酸。此外，该通用协议显示了温和的反应条件，广泛的底物范围和良好的官能团耐受性。根据DFT计算，将自由基加到未活化的烯烃上以平稳地形成新的碳自由基，然后进行1,5-氢原子转移过程（限速步骤），生成更稳定的苄基。Ir对苄基的还原^II种产生相应的苄基碳负离子作为关键中间体，它们进一步受到CO _2的亲核攻击而生成羧酸盐。