Abstract
| - This paper details new copper-catalyzed electrophilic amination reactions of diorganozinc reagents usingO-benzoyl hydroxylamines as electrophilic nitrogen sources that may be accessed in one step. Simpleand functionalized aryl, heteroaryl-, benzyl, n-alkyl, sec-alkyl, and tert-alkyl nucleophiles couple withR2NOC(O)Ph and RHNOC(O)Ph reagents in the presence of catalytic quantities of copper salts to providetertiary and secondary amines, respectively, in generally good yields. In many cases, the product may beisolated analytically pure after a simple extractive workup. The amination process is shown to toleratea significant degree of steric demand. The amination of nominally unreactive Caryl−H bonds via a sequentialdirected ortho metalation/transmetalation/catalytic amination reaction sequence is detailed. The directCu-catalyzed amination of Grignard reagents using cocatalysis by ZnCl2 is described.
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