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A New Method for C−H Functionalization of Aliphatic Compounds by an Unusual Photochemical Reaction of Diazoketones without Elimination of Nitrogen
Author(s) -
Rodina Liudmila L.,
Galkina Olesia S.,
Maas Gerhard,
Platz Matthew S.,
Nikolaev Valerij A.
Publication year - 2016
Publication title -
asian journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.846
H-Index - 44
eISSN - 2193-5815
pISSN - 2193-5807
DOI - 10.1002/ajoc.201600050
Subject(s) - chemistry , tetrahydrofuran , benzophenone , cyclohexane , diazo , photochemistry , diethyl ether , surface modification , ether , nitrogen , nitrogen atom , insertion reaction , organic chemistry , group (periodic table) , catalysis , solvent
Abstract Benzophenone‐sensitized reactions of 4‐diazotetrahydrofuran‐3(2 H )‐ones with H‐donors such as tetrahydrofuran, 1,4‐dioxane, cyclohexane and diethyl ether, occur without elimination of nitrogen and give rise to the corresponding N‐substituted hydrazones or bis‐hydrazonoethanes due to a formal insertion of the terminal N atom of diazo group into α‐C−H bonds of ethers and aliphatic hydrocarbons, with yields of up to 78 %. Long‐wavelength UV irradiation ( λ >310 nm) is most suitable for this process, whereas oxygen molecules adequately quench the triplet excited state of the diazoketone and reduce the preparative yields of C−H‐insertion products. Hence this photochemical reaction of diazoketones can be used for C−H functionalization of different aliphatic compounds.