Monti Andrea, López-Serrano Joaquín, Prieto Auxiliadora, Nicasio M Carmen
Departamento de Química Inorgánica, Universidad de Sevilla, Aptdo 1203, 41071 Sevilla, Spain.
Instituto de Investigaciones Químicas (IIQ), Departamento de Química Inorgánica and Centro de Innovación Química Avanzada (ORFEO-CINQA), Universidad de Sevilla and CSIC, 41092 Sevilla, Spain.
ACS Catal. 2023 Aug 4;13(16):10945-10952. doi: 10.1021/acscatal.3c03166. eCollection 2023 Aug 18.
Among phenol-derived electrophiles, aryl sulfamates are attractive substrates since they can be employed as directing groups for C-H functionalization prior to catalysis. However, their use in C-N coupling is limited only to Ni catalysis. Here, we describe a Pd-based catalyst with a broad scope for the amination of aryl sulfamates. We show that the -methyl-2-aminobiphenyl palladacycle supported by the PCypAr ligand (Cyp = cyclopentyl; Ar = 2,6-bis(2,6-dimethylphenyl)phenyl) efficiently catalyzes the C-N coupling of aryl sulfamates with a variety of nitrogen nucleophiles, including anilines, primary and secondary alkyl amines, heteroaryl amines, -heterocycles, and primary amides. DFT calculations support that the oxidative addition of the aryl sulfamate is the rate-determining step. The C-N coupling takes place through a cationic pathway in the polar protic medium.
在苯酚衍生的亲电试剂中，芳基氨基磺酸酯是有吸引力的底物，因为它们在催化之前可用作C-H官能化的导向基团。然而，它们在C-N偶联中的应用仅限于镍催化。在此，我们描述了一种对芳基氨基磺酸酯胺化具有广泛适用性的钯基催化剂。我们表明，由PCypAr配体（Cyp = 环戊基；Ar = 2,6-双（2,6-二甲基苯基）苯基）支撑的-甲基-2-氨基联苯钯环合物能有效地催化芳基氨基磺酸酯与多种氮亲核试剂的C-N偶联，这些亲核试剂包括苯胺、伯胺和仲烷基胺、杂芳基胺、-杂环以及伯酰胺。密度泛函理论计算支持芳基氨基磺酸酯的氧化加成是速率决定步骤。C-N偶联在极性质子介质中通过阳离子途径发生。
