A transition-metal-free efficient method for the preparation of 1,2,3-trisubstituted benzenes from bispropargyl alcohols and 1,3-dicarbonyl compounds has been developed. The reaction of bispropargyl alcohol with 1,3-dicarbonyl compound proceeds through [3,3]-rearrangement, 6π-electrocyclization, and unexpected Csp 3 −Csp 2 regioselective σ-bond cleavage processes.

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1,3‐Di‐ and 1,2,3‐trisubstituted benzenes are prepared by TfOH‐promoted selective Csp3‐Csp2 σ‐bond cleavage of 1,3‐dicarbonyl compounds in one‐pot.