Regioselectivity of Enzymatic and Photochemical Single Electron Transfer Promoted Carbon-Carbon Bond Fragmentation Reactions of Tetrameric Lignin Model Compounds

Title
Regioselectivity of Enzymatic and Photochemical Single Electron Transfer Promoted Carbon-Carbon Bond Fragmentation Reactions of Tetrameric Lignin Model Compounds
Author(s)
조대원John A. Latham[John A. Latham]박혜정[박혜정]윤웅찬[윤웅찬]Paul Langan[Paul Langan]Debra Dunaway-Mariano[Debra Dunaway-Mariano]Patrick S. Mariano[Patrick S. Mariano]
Keywords
PEROXIDASE-CATALYZED OXIDATION; ASPEN POPULUS-TREMULOIDES; PHANEROCHAETE-CHRYSOSPORIUM; 3,4-DIMETHOXYBENZYL ALCOHOL; MECHANISM; DEGRADATION; CLEAVAGE; PHTHALIMIDES; PATHWAYS; RADICALS
Issue Date
201104
Publisher
AMER CHEMICAL SOC
Citation
JOURNAL OF ORGANIC CHEMISTRY, v.76, no.8, pp.2840 - 2852
Abstract
New types of tetrameric lignin model compounds, which contain the common beta-O-4 and,beta-1 structural subunits found in natural lignins, have been prepared and carbon carbon bond fragmentation reactions of their cation radicals, formed by photochemical (9,10-dicyanoanthracene) and enzymatic (lignin peroxidase) SET-promoted methods, have been explored. The results show that cation radical intermediates generated from the tetrameric model compounds undergo highly regioselective C C bond cleavage in their beta-1 subunits. The outcomes of these processes suggest that, independent of positive charge and odd-electron distributions, cation radicals of lignins formed by SET to excited states of sensitizers or heme-iron centers in enzymes degrade selectively through bond cleavage reactions in beta-1 vs beta-O-4 moieties. In addition, the findings made in the enzymatic studies demonstrate that the sterically large tetrameric lignin model compounds undergo lignin peroxidase-catalyzed cleavage via a mechanism involving preliminary, formation of an enzyme substrate complex.
URI
http://hdl.handle.net/YU.REPOSITORY/25416http://dx.doi.org/10.1021/jo200253v
ISSN
0022-3263
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