The transition state structure for the basic Diels-Alder reaction shows how butadiene and ethene come together to react:

 

 

Pericyclic reactions, like Diels-Alder reactions, and the cycloaddition of two ethenes to form cyclobutane, can be understood by analysing the molecular orbitals of the reactants and products which are involved in the reaction. 

 

 

Analysing the symmetry of the reactant MOs