An enantioselective organocatalytic addition of sodium bisulfite to (E)‐nitroalkenes has been developed by using a chiral bifunctional organocatalyst. The present methodology provides a variety of chiral β‐nitroethanesulfonic acid compounds (17 examples) with excellent results: up to 99 % yield and excellent enantioselectivity (up to 96 % ee). The reaction tolerates (hetero)aryl and alkyl substituents on the β‐nitroalkenes, and β,β‐disubstituted nitroalkenes.

The enantioselective 1,4-alkynylation of conjugated imines derived from saccharin with aryl- and alkyl- substituted terminal alkynes has been achieved. The reaction mediated by diethylzinc in the presence of a catalytic...