Iminoxyl Radical‐Based Strategy for Intermolecular CO Bond Formation: Cross‐Dehydrogenative Coupling of 1,3‐Dicarbonyl Compounds with Oximes

Iminoxyl Radical‐Based Strategy for Intermolecular CO Bond Formation: Cross‐Dehydrogenative Coupling of 1,3‐Dicarbonyl Compounds with Oximes Full article

Journal

Advanced Synthesis & Catalysis
ISSN: 1615-4169 , E-ISSN: 1615-4150

Output data

Year: 2014, Volume: 356, Number: 10, Pages: 2266-2280 Pages count : 15 DOI: 10.1002/adsc.201400143

Authors

Krylov Igor B. ¹ , Terent'ev Alexander O. ¹ , Timofeev Vladimir P. ² , Shelimov Boris N. ¹ , Novikov Roman A. ^1,2 , Merkulova Valentina M. ¹ , Nikishin Gennady I. ¹

Affiliations

1	N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky Prospekt 47, 119991 Moscow, Russian Federation, Fax: (+7)-499–135–5328
2	V. A. Engelhardt Institute of Molecular Biology, Russian Academy of Sciences, 32 Vavilova st., 119991 Moscow, Russian Federation

Cross-dehydrogenative CO coupling of 1,3-diketones and 1,3-keto esters with oximes was realized for the first time. The reaction proceeds in the presence of the oxidants [KMnO4, Mn(OAc)2/KMnO4, Mn(OAc)3⋅2 H2O, MnO2, Mn(acac)3, Fe(ClO4)3, Cu(ClO4)2⋅6 H2O, Cu(NO3)2⋅2.5 H2O, and (NH4)2Ce(NO3)6]. Twenty cross-coupling products were synthesized using potassium permanganate (KMnO4), manganese(II) acetate dihydrate [Mn(OAc)3⋅2 H2O], or the manganese(II) acetate/potassium permanganate [Mn(OAc)2/KMnO4] system; yields are 27–92%. The synthesis can be easily scaled up to gram quantities of the target products. Apparently, the reaction proceeds via a radical mechanism in which the oxidizing agent serves to generate radicals from oximes and perform the one-electron oxidation of 1,3-dicarbonyl compounds. The formation of oxime radicals was confirmed quantitatively by electron spin resonance (ESR) spectroscopy. The coupling described in the present study is the first example of the selective intermolecular reaction involving unstable iminoxyl radicals generated in situ.

Krylov I.B. , Terent'ev A.O. , Timofeev V.P. , Shelimov B.N. , Novikov R.A. , Merkulova V.M. , Nikishin G.I.
Iminoxyl Radical‐Based Strategy for Intermolecular CO Bond Formation: Cross‐Dehydrogenative Coupling of 1,3‐Dicarbonyl Compounds with Oximes
Advanced Synthesis & Catalysis. 2014. V.356. N10. P.2266-2280. DOI: 10.1002/adsc.201400143 WOS Scopus OpenAlex

≡ Web of science:	WOS:000338988800012
≡ Scopus:	2-s2.0-84903817630
≡ OpenAlex:	W2055497097