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Diencs locked in the s-cis configuration will react faster than those able to assume both s-cis and s-trans configurations; those locked in the s-trans conformation will not react.
The reaction is favored (proceeds faster) by the presence of electron withdrawing groups (ie Nitriles, Amines, Carboxylic acids, esters, aldehyde/ketone etc) in the dienophile and electron donating groups (ie methyl ether, alkyl, etc.) in the diene. Diels-Alder reactions are steriospecific (cis-alkenes form cis substituted and trans-alkenes form trans-substituted); this is called syn addition, the configuration of dienophiles is always retained in the product...
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