首页 | 本学科首页   官方微博 | 高级检索  
     检索      


DNA‐Accelerated Catalysis of Carbene‐Transfer Reactions by a DNA/Cationic Iron Porphyrin Hybrid
Authors:Dr Ana Rioz‐Martínez  Dr Jens Oelerich  Dr Nathalie Ségaud  Prof?Dr Gerard Roelfes
Institution:Stratingh Institute for Chemistry, University of Groningen, Groningen, The Netherlands
Abstract: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.
Keywords:carbenes  cyclopropanation  DNA  hybrid catalysts  porphyrins
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号