Conventional hydrofunctionalization of α-olefins with mineral acids proceeds with Markovnikov selectivity to afford branched isomers. The direct formation of linear constitutional isomers is challenging, yet anti-Markovnikov addition would be valuable for the synthesis of commodity chemicals, such as primary alcohols, which are currently only accessible via stoichiometric redox reactions, with a full equivalent of waste of both oxidant and reductant. Strategies that utilize radical intermediates have been demonstrated, but only for activated alkenes, and the direct use of aqueous mineral acids remains elusive. Here we present anti-Markovnikov addition reactions of aqueous hydrochloric and nitric acid to unactivated alkenes. The transformation is enabled by the in situ generation of photoredox-active ion pairs, derived from acridine and the mineral acid, as a combined charge- and phase-transfer catalyst. The introduction of a hydrogen atom transfer catalyst enabled us to bypass the challenging chain propagation by hydrochloric and nitric acids that originates from the high bond dissociation energy.

α-烯烃与无机酸的常规加氢官能化以 Markovnikov 选择性进行，以提供支化异构体。线性结构异构体的直接形成具有挑战性，但反马尔可夫尼科夫加成对合成商品化学品很有价值，例如伯醇，目前只能通过化学计量氧化还原反应获得，完全等量地浪费氧化剂和还原剂。利用自由基中间体的策略已经得到证明，但仅适用于活化的烯烃，直接使用无机酸水溶液仍然难以捉摸。在这里，我们介绍了盐酸和硝酸水溶液与未活化烯烃的反马尔可夫尼科夫加成反应。这种转化是通过原位产生光氧化还原活性离子对实现的，衍生自吖啶和无机酸，作为电荷转移和相转移的组合催化剂。氢原子转移催化剂的引入使我们能够绕过源自高键离解能的盐酸和硝酸具有挑战性的链增长。