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Organocatalytic asymmetric domino sulfa-Michael/aldol condensation reactions between 1,4-dithiane-2,5-diol (the dimer of mercaptoacetaldehyde) and cinnamaldehydes were efficiently promoted by (S)-diphenylprolinol TMS ether in the presence of bile acid derivatives, leading to hitherto unknown 4,5-dihydrothiophene-2-carbaldehydes in moderate to good yields and good enantioselectivities.