Selective cross-dehydrogenative C–O coupling of N-hydroxy compounds with pyrazolones. Introduction of the diacetyliminoxyl radical into the practice of organic synthesis

Selective cross-dehydrogenative C–O coupling of N-hydroxy compounds with pyrazolones. Introduction of the diacetyliminoxyl radical into the practice of organic synthesis Full article

Journal

Organic chemistry frontiers
ISSN: 2052-4110 , E-ISSN: 2052-4129

Output data

Year: 2017, Volume: 4, Number: 10, Pages: 1947-1957 Pages count : 11 DOI: 10.1039/c7qo00447h

Authors

Krylov Igor B. ¹ , Paveliev Stanislav A. ¹ , Shelimov Boris N. ¹ , Lokshin Boris V. ² , Garbuzova Irina A. ² , Tafeenko Viktor A. ³ , Chernyshev Vladimir V. ^4,3 , Budnikov Alexander S. ^1,5 , Nikishin Gennady I. ¹ , Terent'ev Alexander O. ¹

Affiliations

1	N. D. Zelinsky Institute of Organic Chemistry of the Russian Academy of Sciences
2	A. N. Nesmeyanov Institute of Organoelement Compounds of the Russian Academy of Sciences
3	Department of Chemistry, M.V. Lomonosov Moscow State University, 1-3 Leninskie Gory, Moscow 119991, Russian Federation
4	A. N. Frumkin Institute of Physical Chemistry and Electrochemistry RAS, 31 Leninsky prospect, Moscow 119071, Russian Federation
5	Higher Chemical College of the Russian Academy of Sciences,Mendeleev University of Chemical Technology of Russia

Oxidative C–O coupling of pyrazolones with N-hydroxy compounds of different classes (N-hydroxyphthalimide, N-hydroxybenzotriazole, oximes) was achieved; both one-electron oxidants (Fe(ClO4)3, (NH4)2Ce(NO3)6) and two-electron oxidants (PhI(OAc)2, Pb(OAc)4) are applicable, and the yields reach 91%. Apparently, the coupling proceeds via the formation of N-oxyl radicals from N-hydroxy compounds. One of the N-oxyl intermediates, the diacetyliminoxyl radical, was found to be exclusively stable in solution in spite of being sterically unhindered; it was isolated from an oxidant and used as a new reagent for the synthesis and mechanism study. The products of C–O coupling of pyrazolones with N-hydroxyphthalimide can be easily transformed into aminooxy compounds, valuable substances for combinatorial chemistry.

Krylov I.B. , Paveliev S.A. , Shelimov B.N. , Lokshin B.V. , Garbuzova I.A. , Tafeenko V.A. , Chernyshev V.V. , Budnikov A.S. , Nikishin G.I. , Terent'ev A.O.
Selective cross-dehydrogenative C–O coupling of N-hydroxy compounds with pyrazolones. Introduction of the diacetyliminoxyl radical into the practice of organic synthesis
Organic chemistry frontiers. 2017. V.4. N10. P.1947-1957. DOI: 10.1039/c7qo00447h WOS Scopus OpenAlex

Web of science:	WOS:000411716700008
Scopus:	2-s2.0-85030108680
OpenAlex:	W2737052919

DB	Citing
OpenAlex	44
Scopus	40
Web of science	41