Ray S.Gupta N.Singh M.S.2025-01-132025-01-13202415237060https://dl.bhu.ac.in/ir/handle/123456789/2948An operationally simple and highly efficient synthesis of functionalized thiophenes has been developed by LiBr promoted heteroannulation of ?-ketodithioesters and thioamides with bench-stable sulfoxonium ylides in open air for the first time. This one-pot strategy involves formal Csp3-H bond insertion/intramolecular cyclization cascade, featuring readily accessible starting materials, TM and additive-free condition, broad substrate scope, high functional group compatibility, and scalability. Moreover, the carbonyl, thiomethyl, and amino groups in the resulting thiophene provide a good handle on downstream transformations. � 2024 American Chemical Society.enArticle10.1021/acs.orglett.4c03680