In this communication, an efficient asymmetric aminoalkylation of 5‐aminopyrazole derivatives with cyclic benzoxathiazine 2,2‐dioxides catalyzed by a quinine‐derived squaramide in dichloromethane has been established. This is the first example of 5‐aminopyrazole derivatives in asymmetric catalysis. A variety of chiral sulfamidates bearing an aminopyrazole moiety were obtained in good yields (up to 98 %) and moderate to excellent enantioselectivities (up to 99 %ee).

A diastereo- and enantioselective organocatalytic aldol reaction between alkylidenepyrazolones and trifluoromethyl ketones leading to chiral tertiary alcohols bearing a trifluoromethyl group is presented. The methodology is based on the use of a bifunctional organocatalyst in order to activate the γ-hydrogen atoms of the alkylidenepyrazolone nucleophile and the carbonyl group of the trifluoromethylarylketone providing highly functionalized trifluoromethyl alcohols with moderate yields, excellent diastereoselectivity, and moderate to good enantioselectivity. Experiments monitoring the conversion by 1 H NMR and the enantiomeric excess by HPLC with the reaction time showed that full conversion of the starting materials is not achieved and that the enantiomeric excess decreases upon extended times, probably due to the reversibility of the reaction.