1,3‐Butadienyl‐thiocyanate in der Diels ‐ Alder ‐Reaktion mit anschliessender [3,3]‐sigmatroper Umlagerung

1,3‐Butadienyl Thiocyanates in the Diels ‐ Alder Reaction Followed by a [3,3]‐Sigmatropic Shift ( E )‐ and ( Z )‐1,3‐Butadienyl thiocyanates 3 , 4 , and 12–15 have been synthesized selectively. Their use as dienes for Diels ‐ Alder reactions followed by a [3,3]‐sigmatropic shift to obtain an isomeric isothiocyanate has been studied. The butadienyl thiocyanates are, unfortunately, not very reactive in Diels ‐ Alder reactions. This disadvantage can be overcome, if a trapping reaction with EtOH is added to the two‐step sequence. This sequence allows to get good yields of the O ‐ethyl thiocarbamates 18–23 , even if the first two reactions have not favorable equilibrium constants.