Cross-Coupling of aryl Halides with Amides and Carbamates

1 Cross-Coupling of aryl Halides with Amides and Carbamates 

Buchwald s research indicated that vicinal diamines, such as ethylenediamine (EDA, L12), raotra s yclohexanediamine (CyDA, 19), as well as their N, N -dimethyl derivatives (DMEDA, Lll and DMCyDA, LIO), were excellent hgands for the amidation of aryl halides (Table 9.6, entry 1) [21, 31], This catalytic system allowed a wide range of amides (including lactams, open chain alkylamides and arylamides) and carbamates to be coupled with aryl halides. The hindered amides also gave good results. The reaction occurred at about 80-110 °C. Remarkably, DMCyDA (LIO) could even promote the amidation of deactivated aryl chlorides at a Uttle higher reaction temperature (110-130°C). 

Coupling of aryl halides and trifluoroacetamide occurred at 45-75 °C catalyzed by CuI/DMEDA (Lll), followed by in situ hydrolysis to provide the corresponding primary arylamines (entry 2) [32]. The Cul/l,10-phen (L13) catalytic system was found to be able to promote the selective coupling of N-Boc hydrazine [33] (entry 3) and the coupling of N- and O- functionalized hydroxylamines with aryl iodides (entry 4) [34]. Hosseinzadeh and coworkers reported the coupling reaction of aryl iodides with amides catalyzed by CuI/l,10-Phen (L13) by using KF/AI2O3 as the 

a L9-L12 arylamides, alkylamides, lactams, oxazolidinones carbamates Cul, K3PO4 (or CS2CO3) dioxane (or toluene), 80-130 C [21] [31] 

Br L19 lactams, amides 2-hydroxypyridine CuBr, CS2CO3 DMSO, RT-75 C [27] 

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