期刊
CHEMSUSCHEM
卷 8, 期 10, 页码 1768-1778出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/cssc.201500048
关键词
cleavage reactions; homogeneous catalysis; lignin; porphyrinoids; oxidation
资金
- National Science Fund for Distinguished Youth Scholars [21025625]
- Program for Changjiang Scholars and Innovative Research Team in University [IRT1066]
- Major Research Plan of the National Natural Science Foundation of China [21390204]
- National High-Tech Research and Development Plan of China (863 Program) [2012AA021201]
- National Natural Science Foundation of China [21406110]
- Jiangsu Province Natural Science Foundation for Youths [BK20140938]
- State Key Laboratory of Motor Vehicle Biofuel Technology [KFKT2013001]
- Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD)
A series of metallo-deuteroporphyrins derived from hemin were prepared as models of the cytochrome P450 enzyme. With the aid of the highly active CoII deuteroporphyrin complex, the catalytic oxidation system was applied for the oxidation of several lignin model compounds, and high yields of monomeric products were obtained under mild reaction conditions. It was found that the modified cobalt deuteroporphyrin that has no substituents at the meso sites but does have the disulfide linkage in the propionate side chains at the beta sites exhibited much higher activity and stability than the synthetic tetraphenylporphyrin. The changes in the propionate side chains can divert the reactivity of cobalt deuteroporphyrins from the typical C-C bond cleavage to C-O bond cleavage. Furthermore, this novel oxidative system can convert enzymolysis lignin into depolymerized products including a significant portion of well-defined aromatic monomers.
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