Despite the simplicity and abundance of ethylene, its practical application presents significant hurdles due to its nature as a highly flammable gas. Herein, a strategic use of easily handled vinyl ether is reported as a latent ethylene surrogate achieved via a spin-center shift (SCS) pathway, enabling the successful three-component reaction that bridges heteroarenes and various coupling partners, including sulfinates, thiols, and phosphine oxides. Through a photoredox catalytic process, α-oxy radicals are generated by combining various radicals with phenyl vinyl ether, which are subsequently added to N-heteroarenes. Subsequently, the radical-mediated SCS pathway serves as the driving force for C─O bond cleavage, effectively engaging the phenoxy group as a leaving group. In addition, by broadening the utility of the method, a valuable synthon is provided for efficient C─H vinylation of N-heteroarenes following sulfonyl group elimination. This approach not only enriches the toolbox of synthetic methodology but also provides a more streamlined alternative, circumventing the challenges associated with direct ethylene gas usage. The versatility of the method, particularly evident in late-stage functionalizations of medicinally relevant molecules and peptides, underscores its capability to produce invaluable three-component compounds and vinylated N-heteroarene derivatives.

中文翻译：

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通过自旋中心位移揭示乙烯基醚作为杂芳烃 C─H 官能化中乙烯替代物的潜力


尽管乙烯简单且丰富，但由于其高度易燃气体的性质，其实际应用存在重大障碍。据报道，战略性地使用易于处理的乙烯基醚作为通过自旋中心转移（SCS）途径实现的潜在乙烯替代物，从而能够成功地桥接杂芳烃和各种偶联伙伴（包括亚磺酸盐、硫醇和氧化膦。通过光氧化还原催化过程，各种自由基与苯基乙烯基醚结合生成α-氧自由基，随后将其加成到N-杂芳烃中。随后，自由基介导的 SCS 途径作为 C─O 键断裂的驱动力，有效地将苯氧基作为离去基团。此外，通过扩大该方法的实用性，为磺酰基消除后 N-杂芳烃的有效 C─H 乙烯基化提供了有价值的合成子。这种方法不仅丰富了合成方法的工具箱，而且提供了更简化的替代方案，规避了与直接使用乙烯气体相关的挑战。该方法的多功能性，在医学相关分子和肽的后期功能化中尤其明显，强调了其生产宝贵的三组分化合物和乙烯基化 N-杂芳烃衍生物的能力。