Regioselective Reversal Cyclization To Access either Eight-Membered Sulfur-Containing Heterocycle-Fused γ‑Pyrones or 2‑(1,4-Dithianyl)-4-pyrones from the Same Precursors

A regioselective reverse strategy for the construction of eight-membered sulfur-containing heterocycle-fused γ-pyrones and 2-(1,4-dithianyl)-4-pyrones starting from 2-diazo-γ-pyrones and dithioacetals was achieved for the first time. The process combines C–S bond formation via sulfur ylides and C–C bond formation via electron transfer to afford the target molecules in a facile manner with 100% regioselectivity and in excellent isolated yields (up to 90%).