Heteroarylamines are important scaffolds in a wide range of biologically active natural products and pharmaceuticals. Therefore, the versatile and practical protocols for the formation of C(sp2)-N bond have been intensively studied. Recently, Cu catalytic system has been introduced to facilitate electrophilic amination reactions of O-benzoyl hydroxyamines (BzO-NR2) with heteroarylmetal reagents, affording heteroarylamine compounds. Various organometal­ reagents including zincs, magnesiums, borons, and silicons were used for the Cu-catalyzed electrophilic aminations. In this study, we developed a practical and efficient method for the synthesis of heteroarylamines using easily accessible organoaluminum reagents and readily prepared O-benzoyl hydroxyamines in the presence of a low-cost Cu catalyst. The heteroarylaluminum reagents, generated from the direct ortho-lithiation and transmetallation with inexpensive Et2AlCl, can be directly used without further filtration or purification. The Cu catalytic electrophilic amination reactions with low catalyst loading (1~3 mol%) proceeded to complete conversion within 30 min to provide the desired heteroarylamines with high yields.

Cu-catalyzed one-pot electrophilic amination with heteroarylaluminum reagents

249th National Meeting (2015)

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