A New Method for C-H Functionalization of Aliphatic Compounds by an Unusual Photochemical Reaction of Diazoketones without Elimination of Nitrogen

Benzophenone-sensitized reactions of 4-diazotetrahydrofuran-3(2H)-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 insertio...

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Published inAsian journal of organic chemistry Vol. 5; no. 5; pp. 691 - 698
Main Authors Rodina, Liudmila L., Galkina, Olesia S., Maas, Gerhard, Platz, Matthew S., Nikolaev, Valerij A.
Format Journal Article
LanguageEnglish
Published WEINHEIM Wiley 01.05.2016
Subjects
Chemistry
Chemistry, Organic
Physical Sciences
Science & Technology
aminals
ALPHA-DIAZOCARBONYL COMPOUNDS
SERIES
AZIDES
DIAZO KETONES
C-H functionalization
YLIDES
photosensitization
WOLFF REARRANGEMENT
CHEMISTRY
N BOND FORMATION
diazo compounds
PHOTOLYSIS
DERIVATIVES
hydrazones
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Summary:Benzophenone-sensitized reactions of 4-diazotetrahydrofuran-3(2H)-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 alpha-C-H bonds of ethers and aliphatic hydrocarbons, with yields of up to 78%. Long-wavelength UV irradiation (lambda > 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.
ISSN:2193-5807
2193-5815
DOI:10.1002/ajoc.201600050