Abstract
N-Phenylmaleimide undergoes Diels–Alder cycloaddition predominantly to the face of cis-cyclohexa-3,5-diene-1,2-diol (3) syn to the oxygen functions. Derivatization can be used to alter the π-facial diastereoselectivity in a synthetically useful manner. The best cases are the exclusive, high yield, production of the syn-addition product with the trimethylsilyl ether derivative (8), and the exo-benzylidine derivative (26) gave a 96:4 anti/syn ratio of adducts.

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