Asymmetric cross-aldol reactions of -keto hydrazones and ,-unsaturated -keto hydrazones with trifluoromethyl ketones

alpha-Keto hydrazones and alpha,beta-unsaturated gamma-keto hydrazones are suitable pro-nucleophiles for asymmetric cross-aldol reactions with trifluoromethyl ketones via aza-di(tri)enamine-type intermediates. A quinidine-derived primary amine catalyst affords tertiary trifluoromethylated alcohols in good-to-excellent yields and high enantioselectivities. Subsequent transformations of hydrazono moieties yield appealing fluorinated carboxylic acids, 1,4-dicarbonyls and gamma-keto acids.