期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 55, 期 45, 页码 14136-14140出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201608121
关键词
carbenes; cyclopropanation; DNA; hybrid catalysts; porphyrins
资金
- NRSC-Catalysis
- European Research Council (ERC) [280010]
- Ramon Areces Foundation
- Netherlands Ministry of Education, Culture, and Science Gravitation program [024.001.035]
- European Research Council (ERC) [280010] Funding Source: European Research Council (ERC)
A novel DNA-based hybrid catalyst comprised of salmon testes DNA and an iron(III) complex of a cationic meso-tetrakis(N-alkylpyridyl)porphyrin was developed. When the N-methyl substituents were placed at the ortho position with respect to the porphyrin ring, high reactivity in catalytic carbene-transfer reactions was observed under mild conditions, as demonstrated in the catalytic enantioselective cyclopropanation of styrene derivatives with ethyl diazoacetate (EDA) as the carbene precursor. A remarkable feature of this catalytic system is the large DNA-induced rate acceleration observed in this reaction and the related dimerization of EDA. It is proposed that high effective molarity of all components of the reaction in or near the DNA is one of the key contributors to this unique reactivity. This study demonstrates that the concept of DNA-based asymmetric catalysis can be expanded into the realm of organometallic chemistry.
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