Journal
JOURNAL OF ORGANIC CHEMISTRY
Volume 75, Issue 19, Pages 6549-6562Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jo1012509
Keywords
-
Categories
Funding
- U.S. Department of Energy [20080001DR]
- Korean government [2009-0072585]
- National Research Foundation of Korea [2009-0072585] Funding Source: Korea Institute of Science & Technology Information (KISTI), National Science & Technology Information Service (NTIS)
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [0946690] Funding Source: National Science Foundation
Ask authors/readers for more resources
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.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available