Full Cleavage of C≡C Bond in Electron-Deficient Alkynes via Reaction with Ethylenediamine
Sergei F. Vasilevsky A D , Maria P. Davydova A , Victor I. Mamatyuk B , Nikolay Tsvetkov C , Audrey Hughes C , Denis S. Baranov A and Igor V. Alabugin C D
+ Author Affiliations
- Author Affiliations
A Voevodsky Institute of Chemical Kinetics and Combustion, Siberian Branch of the Russian Academy of Science, 3 Institutskaya Street, Novosibirsk 630090, Russia.
B Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch of the Russian Academy of Science, Novosibirsk 630090, Russia.
C Department of Chemistry and Biochemistry, Florida State University, Tallahassee, FL 32306, USA.
D Corresponding authors. Email: vasilev@kinetics.nsc.ru; alabugin@chem.fsu.edu
Australian Journal of Chemistry 70(4) 421-429 https://doi.org/10.1071/CH17026
Submitted: 12 January 2017 Accepted: 11 February 2017 Published: 9 March 2017
Abstract
Reaction of 1,2-diaminioethane (ethylenediamine) with electron-deficient alkynes leads to full scission of the C≡C bond even in the absence of a keto group directly attached to the alkyne. This process involves oxidation of one of the alkyne carbons into C2 of a 2-R-4,5-dihydroimidazole with the concomitant reduction of the other carbon to a methyl group. The sequence of Sonogashira coupling with the ethylenediamine-mediated fragmentation described in this work can be used for selective formal substitution of halogen in aryl halides by a methyl group or a 4,5-dihydroimidazol-2-yl moiety.
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