C═N Bond Ozonolysis and β-Scission: A Breakthrough Approach to the Synthesis of ω-Functionalized Compounds from Carbonyl Derivatives.

Autor: Fomenkov DI; N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky prosp., Moscow 119991, Russian Federation., Budekhin RA; N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky prosp., Moscow 119991, Russian Federation., Radulov PS; N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky prosp., Moscow 119991, Russian Federation., Fomenkov AI; N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky prosp., Moscow 119991, Russian Federation., He LN; State Key Laboratory and Institute of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin 300071, China., Yaremenko IA; N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky prosp., Moscow 119991, Russian Federation., Terent'ev AO; N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky prosp., Moscow 119991, Russian Federation.
Jazyk: angličtina
Zdroj: Organic letters [Org Lett] 2024 Sep 27; Vol. 26 (38), pp. 8095-8099. Date of Electronic Publication: 2024 Sep 16.
DOI: 10.1021/acs.orglett.4c02999
Abstrakt: This work discloses a two-step, one-pot approach to ω-functionalized esters via cleavage of the alicyclic fragment of cycloalkanone semicarbazones. This approach is based on a combination of the synthesis of various alkoxyhydroperoxides via cycloalkanone semicarbazone ozonolysis and in situ interaction of these peroxides with transition metal salts, leading to cleavage of the aliphatic cycle and subsequent ω-functionalized ester formation. A broad series of ω-halogen or pseudohalogen esters have been successfully synthesized in yields ranging from 23 to 73% per starting semicarbazone. A major advantage of the approach is the ability to use different cycloalkanone semicarbazones, including those with large cycles and substituents in them. The possibility of carrying out ozonolysis in the presence of various alcohols makes it possible to obtain the corresponding esters of ω-substituted carboxylic acids.
Databáze: MEDLINE
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