3-sulfolene is mainly valued as a stand-in for butadiene.  The in situ production and immediate consumption of 1,3-butadiene largely avoids contact with the diene, which is a gas at room temperature. One potential drawback, aside from expense, is that the evolved sulfur dioxide can cause side reactions with acid-sensitive substrates.
Diels-Alder reaction between 1,3-butadiene and dienophiles of low reactivity usually requires prolonged heating above 100 °C. Such procedures are rather dangerous. If neat butadiene is used, special equipment for work under elevated pressure is required. With sulfolene no buildup of butadiene pressure could be expected as the liberated diene is consumed in the cycloaddition, and therefore the equilibrium of the reversible extrusion reaction acts as an internal "safety valve".
3-Sulfolene reacts with maleic anhydride in boiling xylene to cis-4-cyclohexene-1,2-dicarboxylic anhydride, obtaining yields of up to 90%.
3-Sulfolene reacts also with dienophiles in trans configuration (such as diethyl fumarate) at 110 °C with SO elimination in 66–73% yield to the trans-4-cyclohexene-1,2-dicarboxylic diethyl ester.
6,7-Dibromo-1,4-epoxy-1,4-dihydronaphthalene (6,7-Dibromonaphthalene-1,4-endoxide, accessible after debromination from 1,2,4,5-tetrabromobenzene using an equivalent of n-butyllithium and Diels-Alder reaction in furan in 70% yield) reacts with 3-sulfolene in boiling xylene to give a tricyclic adduct. This precursor yields, after treatment with perchloric acid, a dibromo dihydroanthracene which is dehydrogenated in the last step with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) to 2,3-dibromoanthracene.
1,3-Butadiene (formed in the retro-cheletrophic reaction of 3-sulfolene) reacts with dehydrobenzene (benzyne, obtained by thermal decomposition of benzenediazonium-2-carboxylate) in a Diels-Alder reaction in 9% yield to give 1,4-dihydronaphthalene.