期刊
ACS CATALYSIS
卷 12, 期 19, 页码 12246-12252出版社
AMER CHEMICAL SOC
DOI: 10.1021/acscatal.2c03424
关键词
oxidation; C-H activation; biocatalysis; redox mediator; green chemistry
资金
- Office of the Vice Chancellor for Research and Graduate Education at the University of Wisconsin - Madison
- Wisconsin Alumni Research Foundation
- National Institute of General Medical Sciences of the National Institutes of Health [CHE-1048642]
- UW - Madison Hilldale Fellowship
- NSF
- Bender Fund
- [T32GM008505]
Enzyme-mediator systems, such as the horseradish peroxidase (HRP), H2O2, and N-hydroxyphthalimide (NHPI) system, are effective for the functionalization of alkylbenzenes. The HRP-NHPI system shows superior activity compared to existing enzyme-mediator systems, converting alkylbenzenes to ketones and aldehydes. This system operates under mild conditions and can be used in aqueous-organic solvent mixtures. It also enables the conversion of alkylbenzenes to benzylic amines in a one-pot, two-step enzymatic cascade.
Enzyme-mediator systems generate radical inter-mediates that abstract hydrogen atoms under mild conditions. These systems have been employed extensively for alcohol oxidation, primarily in biomass degradation, but they are underexplored for direct activation of C(sp3)-H bonds in alkyl groups. Here, we combine horseradish peroxidase (HRP), H2O2, and redox mediator N-hydroxyphthalimide (NHPI) for C(sp3)-H functionalization of alkylbenzene-type substrates. The HRP- NHPI system is >10-fold more active than existing enzyme- mediator systems in converting alkylbenzenes to ketones and aldehydes under air, and it operates from 0-50 degrees C and in numerous aqueous-organic solvent mixtures. The benzylic substrate radical can be trapped through a reaction with NHPI, demonstrating the formation of benzylic products beyond ketones. Furthermore, we demonstrate a one-pot, two-step enzymatic cascade for converting alkylbenzenes to benzylic amines. Overall, the HRP-NHPI system enables the selective benzylic C-H functionalization of diverse substrates under mild conditions using a straightforward procedure.
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