Visible-Light-Induced Metal- and Photocatalyst-Free Radical Cascade Cyclization of Cinnamamides for Synthesis of Functionalized Dihydroquinolinones
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Date
2023-07-18T00:00:00
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Publisher
American Chemical Society
Abstract
Visible-light-promoted metal- and photocatalyst-free radical cascade cyclization of cinnamamides with ?-oxocarboxylic acids is described for sustainable synthesis of diverse pharmaceutically important dihydroquinolinone scaffolds in one pot under mild conditions. The decarboxylative cascade cyclization proceeded efficiently at room temperature without the need for expensive photocatalysts such as Ir or Ru complexes, which indicates the practicability and environmentally benign nature of this protocol. Preliminary mechanistic studies reveal that the blue LED irradiation efficiently cleaves the I-O bond of the hypervalent iodine reagent PhI(O2CCOAr)2 formed through ligand exchange between iodobenzene diacetate and arylglyoxylic acid to initiate the cascade reaction. The synthetic value of this operationally simple and energy-efficient method is further demonstrated by late-stage functionalization of drug molecules in excellent yields. � 2023 American Chemical Society.
Description
Keywords
Cyclization, Energy efficiency, Iridium compounds, Ruthenium compounds, Scaffolds, 1 benzyl 3 (4 bromobenzoyl) 4 phenyl 3,4 dihydroquinolin 2(1h) one, 1 methyl 3 (2 methylbenzoyl) 4 phenyl 3,4 dihydroquinolin 2(1h) one, 1 methyl 3 (4 methylbenzoyl) 4 phenyl 3,4 dihydro 1,8 naphthyridin 2(1h) one, 1 methyl 3 (4 methylbenzoyl) 4 phenyl 3,4 dihydroquinolin 2(1h) one, 1 methyl 4 phenyl 3 (thiophene 2 carbonyl) 3,4 dihydroquinolin 2(1h) one, 1 methyl 4 phenyl 3 [4 (trifluoromethyl)benzoyl] 3,4 dihydroquinolin 2(1h) one, 2 [3 (4 bromobenzoyl) 2 oxo 4 phenyl 3,4 dihydroquinolin 1(2h) yl]ethyl 2 (6 methoxynaphthalen 2 yl)propanoate, 2 [3 (4 methylbenzoyl) 2 oxo 4 phenyl 3,4 dihydroquinolin 1(2h) yl]ethyl 2 (6 methoxynaphthalen 2 yl)propanoate, 3 (4 bromobenzoyl) 1 ethyl 4 phenyl 3,4 dihydroquinolin 2(1h) one, 3 (4 bromobenzoyl) 1 methyl 4 phenyl 3,4 dihydroquinolin 2(1h) one, 3 (4 bromobenzoyl) 6 fluoro 4 (2 methoxyphenyl) 1 methyl 3,4 dihydroquinolin 2(1h) one, 3 (4 bromobenzoyl) 6 methoxy 1 methyl 4 (4 tolyl) 3,4 dihydroquinolin 2(1h) one, 3 (4 methoxybenzoyl) 1 methyl 4 phenyl 3,4 dihydroquinolin 2(1h) one, 3 acetyl 1 methyl 4 phenyl 3,4 dihydroquinolin 2(1h) one, 3 benzoyl 1 ethyl 4 phenyl 3,4 dihydroquinolin 2(1h) one, 3 benzoyl 1 methyl 4 phenyl 3,4 dihydroquinolin 2(1h) one, 3 benzoyl 1,5,7 trimethyl 4 phenyl 3,4 dihydroquinolin 2(1h) one, 3 benzoyl 4 (4 bromo 2 fluorophenyl) 1,5,7 trimethyl 3,4 dihydroquinolin 2(1h) one, 3 benzoyl 6 bromo 1,5 dimethyl 4 phenyl 3,4 dihydroquinolin 2(1h) one, 3 benzoyl 6 fluoro 1 methyl 4 phenyl 3,4 dihydroquinolin 2(1h) one, 3 benzoyl 6 fluoro 4 (2 methoxyphenyl) 1 methyl 3,4 dihydroquinolin 2(1h) one, 3 benzoyl 6 methoxy 1 methyl 4 phenyl 3,4 dihydroquinolin 2(1h) one, 4 (2,3 dimethoxyphenyl) 6 fluoro 3 (4 methoxybenzoyl) 1 methyl 3,4 dihydroquinolin 2(1h) one, 4 (4 bromo 2 fluorophenyl) 1,5,7 trimethyl 3 (4 methylbenzoyl) 3,4 dihydroquinolin 2(1h) one, 4 (4 bromo 2 fluorophenyl) 1,5,7 trimethyl 3 [4 (trifluoromethyl)benzoyl] 3,4 dihydroquinolin 2(1h) one, 6 methoxy 3 (4 methoxybenzoyl) 1 methyl 4 phenyl-3,4 dihydroquinolin 2(1h) one, 6 methyl 8 (4 methylbenzoyl) 9 [3 (trifluoromethyl)phenyl] 2,3,8,9 tetrahydro[1,4]dioxino[2,3 g]quinolin 7(6h) one, 8 (3,4 dimethoxybenzoyl) 6 methyl 9 [3 (trifluoromethyl)phenyl] 2,3,8,9 tetrahydro[1,4]dioxino[2,3 g]quinolin 7(6h) one, 8 benzoyl 6 (prop 2 yn 1 yl) 9 [3 (trifluoromethyl)phenyl] 2,3,8,9 tetrahydro[1,4]dioxino[2,3 g]quinolin 7(6h) one, 8 benzoyl 6 methyl 9 [3 (trifluoromethyl)phenyl] 2,3,8,9 tetrahydro[1,4]dioxino[2,3 g]quinolin 7(6h) one, acetoacetic acid, amide, carboxylic acid derivative, cinnamic acid derivative, dihydroquinoline derivative, ethyl 2 (3 benzoyl 2 oxo 4 phenyl 3,4 dihydroquinolin 1 (2h) yl]acetate, ethyl 2 [3 benzoyl 4 (4 bromo 2 fluorophenyl) 5,7 dimethyl 2 oxo 3,4 dihydroquinolin 1(2h) yl]acetate, ethyl 2 [4 (4 bromo 2 fluorophenyl) 5,7 dimethyl 3 (4 methylbenzoyl) 2 oxo 3,4 dihydroquinolin 1(2h) yl]acetate, free radical, functional group, glyoxylic acid, iodine, iodobenzene, iridium complex, ligand, metal, n methyl 2 [3 (4 methylbenzoyl) 2 oxo 4 phenyl 3,4 dihydroquinolin 1(2h) yl] n [3 phenyl 3 [4 (trifluoromethyl)phenoxy]propyl]acetamide, phenylglyoxylic acid, reagent, ruthenium complex, unclassified drug, Cascade cyclization, Condition, Environmentally benign, Functionalized, Ir complexes, Mechanistic studies, One pot, Ru complexes, Visible light, Visible light induced, Article, chemical bond, complex formation, conjugation, controlled study, cyclization, decarboxylation, drug synthesis, electrophilicity, one pot synthesis, photocatalysis, reaction analysis, reaction optimization, regioselectivity, room temperature, Free radicals