The development of sustainable oxidation chemistry demands strategies to harness O₂ as a terminal oxidant. Oxidase catalysis, in which O₂ serves as a chemical oxidant without necessitating incorporation of oxygen into reaction products, would allow diverse substrate functionalization chemistry to be coupled to O₂ reduction. Direct O₂ utilization suffers from intrinsic challenges imposed by the triplet ground state of O₂ and the disparate electron inventories of four-electron O₂ reduction and two-electron substrate oxidation. Here, we generate hypervalent iodine reagents—a broadly useful class of selective two-electron oxidants—from O₂. This is achieved by intercepting reactive intermediates of aldehyde autoxidation to aerobically generate hypervalent iodine reagents for a broad array of substrate oxidation reactions. The use of aryl iodides as mediators of aerobic oxidation underpins an oxidase catalysis platform that couples substrate oxidation directly to O₂ reduction. We anticipate that aerobically generated hypervalent iodine reagents will expand the scope of aerobic oxidation chemistry in chemical synthesis.

可持续氧化化学的发展要求采取O ₂作为终端氧化剂的策略。氧化酶催化（其中O ₂用作化学氧化剂，而无需将氧气掺入反应产物中）将使各种底物官能化化学反应与O ₂还原反应耦合。直接ø ₂从通过的O-三重基态施加固有的挑战利用率患有₂和四电子的O相异电子库存₂还原和两电子底物氧化。在这里，我们从O ₂生成高价碘试剂（一种广泛使用的选择性二电子氧化剂）。。这是通过截留醛自氧化的反应性中间体以有氧方式产生用于多种底物氧化反应的高价碘试剂来实现的。使用芳基碘化物作为有氧氧化的介体可加强氧化酶催化平台的作用，该平台可将底物氧化直接耦合至O ₂还原。我们预计，需氧产生的高价碘试剂将扩大化学合成中有氧氧化化学的范围。