Consecutive photoinduced electron transfer (ConPET) is a powerful and atom‐economical protocol to overcome the limitations of the intrinsic redox potential of visible light‐absorbing photosensitizers, thereby considerably improving the substrate and reaction types. Likely because such an exothermic single‐electron transfer (SET) process usually does not require the aid of chiral catalysts, resulting in an inevitable racemic background reaction, notably, no enantioselective manifolds have been reported. Herein, we report on the viability of cooperative ConPET and chiral hydrogen‐bonding catalysis for the [3 + 2] photocycloaddition of cyclopropyl ketones with vinylazaarenes. In addition to enabling the first use of olefins that preferentially interact with chiral catalysts, this catalysis platform paves the way for the efficient synthesis of pharmaceutically and synthetically important cyclopentyl ketones functionalized by azaarenes with high yields, ees and dr. The robust capacity of the method can be further highlighted by the low loading of the chiral catalyst (1.0 mol%), the good compatibility of both 2‐azaarene and 3‐pyridine‐based olefins, and the successful concurrent construction of three stereocenters on cyclpentane rings involving an elusive but important all‐carbon quaternary.

中文翻译：

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通过连续光诱导电子转移实现环丙基酮与乙烯基氮杂芳烃的催化不对称氧化还原中性 [3 + 2] 光环加成

连续光诱导电子转移（ConPET）是一种强大且原子经济的方案，可以克服可见光吸收光敏剂固有氧化还原电位的限制，从而显着改善底物和反应类型。可能是因为这种放热的单电子转移（SET）过程通常不需要手性催化剂的帮助，导致不可避免的外消旋背景反应，值得注意的是，没有对映选择性流形的报道。在此，我们报告了协同ConPET和手性氢键催化在环丙基酮与乙烯基氮杂芳烃的[3 + 2]光环加成反应中的可行性。除了首次使用优先与手性催化剂相互作用的烯烃外，该催化平台还为高效合成药物和合成上重要的由氮杂芳烃官能化的环戊基酮铺平了道路，具有高收率、ee和dr。手性催化剂的低负载量（1.0 mol%）、2-氮杂芳烃和3-吡啶基烯烃的良好相容性以及在环戊烷上成功同时构建三个立体中心，进一步凸显了该方法的强大能力涉及难以捉摸但重要的全碳四元环。