OXIDATIVE INTRAMOLECULAR COUPLING OF AMIDOCUPRATES AS A NOVEL ROUTE TO AMINES AND HYDRAZINES

Amidocuprates, derived from organocopper reagents and lithium amides u pon exposure to oxygen at low temperature, provide new amine derivativ es in satisfactory yields. Details of this flexible and simple methodo logy are given. The reaction mechanism is analyzed in terms of an oxid ative intramolecular coupling of aminyl radicals with the ligands on C u in the intermediate amidocuprate. This reaction is a mild and effici ent method for N-alkylation, -vinylation, and -arylation by which a nu mber of amines, not easily accessible by normal routes, can be synthes ized. Once applied to lithium hydrazides, it also provides a new and s traightforward entry to N-substituted hydrazines.