Stereoselective Electrophilic Amination with Sulfonyloxycarbamates and Azodicarboxylates

3 Stereoselective Electrophilic Amination with Sulfonyloxycarbamates and Azodicarboxylates 

Jean-Pierre Genet, Christine Greek and Damien Lavergne 

Sulfonyl azides 3 allow the introduction of an NH2+ synthon, and alkyl or aryl azides prepared with these reagents can be reduced or hydrolyzed to primary amines, [Id, 2], 

Azodicarboxylates 4 have been used in the electrophilic reaction with diethyl malonate since 1924 [3] however only recently were these reagents recognized as particularly useful for the introduction of an amino moiety after hydrogenolysis of the hydrazide adduct [3], More recently, chloro nitroso reagents of type 5 have been introduced by Oppolzer [4]. These reagents are particularly reactive, giving 

Finally, other N-protected electrophilic reagents should be mentioned such as the N-protected oxaziridines 8 [7], which so far transfer efficiently under mild conditions its N-protected fragment to N-nucleophiles but however give moderate yields with C-nucleophiles, [7c, e]. 

---