The asymmetric construction of all-carbon quaternary centres within acyclic settings represents a long-standing challenge for synthetic chemists. Alongside polar and radical methods, rearrangement reactions represent an attractive platform, but still broadly applicable methods are in high demand. Here we report an asymmetric, radical sulfinyl-Smiles rearrangement to access acyclic amides that bear an α-all-carbon quaternary centre. Our strategy uses enantioenriched N-arylsulfinyl acrylamides as acceptors for a variety of radicals produced in situ under mild photoredox conditions. The sulfinamido group not only directs the 1,4-migration of the aryl moiety onto the α-carbon of the amide, which thus governs its absolute configuration, but also functions as a traceless chiral auxiliary. The amides obtained in this multicomponent process are prevalent in pharmaceuticals, agrochemicals and bioactive natural products, and can be transformed into valuable chiral α,α-disubstituted acids, oxindoles as well as into β,β-disubstituted amines, highlighting the synthetic potential of this transformation.

在无环环境中全碳四元中心的不对称构造是合成化学家长期面临的挑战。除了极性和自由基方法外，重排反应代表了一个有吸引力的平台，但仍然需要广泛适用的方法。在这里，我们报告了一种不对称的自由基亚磺酰基-Smiles 重排，以获得具有 α-全碳四元中心的无​​环酰胺。我们的策略使用对映体富集的N-芳基亚磺酰基丙烯酰胺作为在温和光氧化还原条件下原位产生的各种自由基的受体。亚磺酰胺基不仅指导芳基部分的 1,4-迁移到酰胺的 α-碳上，从而控制其绝对构型，而且还用作无痕手性助剂。在这种多组分工艺中获得的酰胺普遍存在于药物、农用化学品和生物活性天然产物中，并且可以转化为有价值的手性 α,α-二取代酸、羟吲哚以及 β,β-二取代胺，突出了其合成潜力转型。