Condition-Controlled Divergent Synthesis Sulfur-Containing Ester Derivatives from 3 <i>H</i> -Benzo[ <i>c</i> ][1,2]dithiol-3-one and 3-Arylprop-2-yn-1-ols

We report an efficient, one-pot, condition-controlled divergent synthesis strategy through nucleophilic cyclization or Meyer–Schuster rearrangement pathways to construct C–S and C–O bonds for the synthesis of sulfur-containing esters by the opposite reaction conditions (Lewis acid or Brønsted base catalyst). One pathway proceeds with a Brønsted base catalyzed nucleophilic cyclization, affording ( Z )-2-benzylidene-2,3-dihydro-5 H -benzo[ e ][1,4]oxathiepin-5-ones in moderate to excellent yields (DBU, PPh 3, MeCN, 90 °C, 1 h). Another route involves Lewis acid catalyzed Meyer–Schuster rearrangement to form 3-phenylprop-2-yn-1-yl 2-((3-oxo-3-phenylpropyl)thio)benzoates in moderate to good yields (Fe(OTf) 2, Tf 2 O, PPh 3, dioxane, 80 °C, 3 h). The “condition-controlled” strategy offers a novel and selective approach to organic synthesis, significantly enriching the synthetic methodology of sulfur-containing esters.