Amidocuprate

For the synthesis of primary amines, the diester 264 is magnesiated with TMPMgCl LiCl and transmetalated with CuCl 2LiCl, affording the corresponding arylcopper derivative 265. Addition of LiHMDS furnishes the corresponding amidocuprate, which is reacted... 

R2= Me, TMS(CH2)2, p-Tol, 4-N02C6H4, 4-MeOC6H4, 4-CI-C6H4 Fig. 79 Cu(II)-catalyzed tandem amidocupration/radical cyclization reactions... 

All these reactions proceed by initial base-promoted formation of copper amide complexes 306A from diarylamines or sulfonamides 306 or 308, respectively, which are subject to a concerted, sv -amidocupration with the adjacent alkene unit via transition state 306B (Fig. 82). The resulting alkylcopper(II) intermediates 306C are... 

Fig. 80 Copper-catalyzed amidocupration/radical oxygenation reactions...

Group-selective cyclizations to aryl units (306c >307c) indicated that the initial intramolecular amidocupration leads to equatorially oriented radicals, which cyclized to... 

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