Abstract Although allylic thiocyanates undergo a facile thermal (3, 3) isomerization to form the more stable allylic isothiocyanates1, this transformation has played a surprisingly minor role in organic synthesis. We have found that α, β-unsaturated esters (1) can be converted to α-isothiocyanatoacrylic esters (2) via an allylic (3, 3) thiocyanate isomerization.