Theoretical study on the mechanism of Ag-catalyzed synthesis of 3-alkylideneoxindoles from N-aryl-α-diazoamides: a Lewis acid or Ag-carbene pathway?
The mechanism of the title reaction is found to consist of three steps by DFT calculations: (1) N(2) dissociation, (2) intramolecular Ag-carbene addition, and (3) proton transfer. The N(2) dissociation is turnover determining. The product 3-alkylideneoxindole is favored in tautomerization with 3-acetyl-2-hydroxyindole.
Department of Applied Chemistry, China Agricultural University, Beijing, China. lizhe@cau.edu.cn
Zhe
Z
Li
Hai-Xiang
HX
Gao
D000577:Amides / Q000737:chemistry*; D001391:Azo Compounds / Q000737:chemistry; D002384:Catalysis; D003500:Cyclization; D007211:Indoles / Q000138:chemical synthesis* / Q000737:chemistry; D058116:Lewis Acids / Q000737:chemistry*; D008697:Methane / Q000031:analogs & derivatives* / Q000737:chemistry; D008958:Models, Molecular; D009584:Nitrogen / Q000737:chemistry; D000078183:Oxindoles; D011789:Quantum Theory; D012834:Silver / Q000737:chemistry*
D000577:Amides; D001391:Azo Compounds; D007211:Indoles; D058116:Lewis Acids; D000078183:Oxindoles; C022960:2-oxindole; C030011:carbene; D012834:Silver; D009584:Nitrogen; D008697:Methane