Nature and Kinetic Analysis of Carbon-Carbon Bond Fragmentation Reactions of Cation Radicals Derived from SET-Oxidation of Lignin Model Compounds

Title
Nature and Kinetic Analysis of Carbon-Carbon Bond Fragmentation Reactions of Cation Radicals Derived from SET-Oxidation of Lignin Model Compounds
Author(s)
조대원Ramakrishnan Parthasarathi[Ramakrishnan Parthasarathi]Adam S. Pimentel[Adam S. Pimentel]Gabriel D. Maestas[Gabriel D. Maestas]박혜정[박혜정]윤웅찬[윤웅찬]Debra Dunaway-Mariano[Debra Dunaway-Mariano]S. Gnanakaran[S. Gnanakaran]Paul Langan[Paul Langan]Patrick S. Mariano[Patrick S. Mariano]
Keywords
PHOTOSENSITIZED ELECTRON-TRANSFER; SINGLET OXYGEN DEGRADATION; BETA-GUAIACYL ETHER; PHANEROCHAETE-CHRYSOSPORIUM BURDS; PEROXIDASE-CATALYZED OXIDATION; VERATRYL ALCOHOL OXIDATION; ASPEN POPULUS-TREMULOIDES; WHITE-ROT FUNGI; C-C BONDS; MESOLYTIC SCISSION
Issue Date
201010
Publisher
AMER CHEMICAL SOC
Citation
JOURNAL OF ORGANIC CHEMISTRY, v.75, no.19, pp.6549 - 6562
Abstract
Features of the oxidative cleavage reactions of diastereomers of dimeric lignin model compounds, which are models of the major types of structural units found in the lignin backbone, were examined. Cation radicals of these substances were generated by using SET-sensitized photochemical and Ce(IV) and lignin peroxidase promoted oxidative processes, and the nature and kinetics of their C C bond cleavage reactions were determined. The results show that significant differences exist between the rates of cation radical C1-C2 bond cleavage reactions of 1,2-diaryl-(beta-1) and 1-aryl-2-aryloxy(beta-O-4) propan-1,3-diol structural units found in lignins. Specifically, under all conditions C1-C2 bond cleavage reactions of cation radicals of the beta-1 models take place more rapidly than those of the beta-O-4 counterparts. The results of DFT calculations on cation radicals of the model compounds show that the C1-C2 bond dissociation energies of the beta-1 lignin model compounds are significantly lower than those of the beta-O-4 models, providing clear evidence for the source of the rate differences.
URI
http://hdl.handle.net/YU.REPOSITORY/23500http://dx.doi.org/10.1021/jo1012509
ISSN
0022-3263
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