Asymmetric Hydroazidation of Nitroalkenes Promoted by a Secondary Amine-Thiourea Catalyst

Chiral β‐nitro azides are obtained by asymmetric addition of azides to nitroalkenes, with an enantioselectivity of up to 82% ee. The reaction, promoted by an easily accessible secondary amine‐thiourea catalyst, is performed with azidotrimethylsilane in the presence of benzoic acid. Products with different aliphatic β‐substituents are obtained in good yields and with the highest enantioselectivity reported to date. The presence of a secondary amine group was found to be crucial to achieve high stereocontrol.