Abstract

An operationally simple, efficient and convenient approach for the synthesis of highly substituted thiophene frameworks has been developed via the organoindium mediated coupling of α-enolic dithioesters and C2–C3 centres of propargylic bromides. The in situ generated propargyl indium species efficiently guides the unusual mode of fusion through an unprecedented Csp3–S cross-coupling/migratory C-allenylation/thioannulation cascade to furnish the corresponding thiophenes in a single synthetic operation. Furthermore, this protocol does not require any co-catalyst or activator.

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