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Acid‐catalyzed decomposition and stability of diazofuranones: Experimental and mechanistic study
Author(s) -
Semenok Dmitrii,
Mereshchenko Andrey S.,
Medvedev Jury,
Visentin Giorgio
Publication year - 2020
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.4038
Subject(s) - chemistry , regioselectivity , nucleophile , catalysis , aryl , decomposition , alkyl , density functional theory , solvent , computational chemistry , medicinal chemistry , reaction mechanism , solvent effects , organic chemistry
Reactions of substituted 4‐diazotetrahydrofurane‐3‐ones with various acids (p K a < 3) irrespective of acid strength give rise to elimination of nitrogen with subsequent 1,2‐nucleophilic migration of aryl (alkyl) groups from C‐5 to C‐4 position of heterocyclic core with quantitative formation of regioisomeric 3(2 Н )furanones (yields up to 99%). Regioselectivity of this acid‐catalyzed process increases with the decreasing of solvent polarity and strongly depends on the nature of substituents in the aryl groups. The suggested mechanism of this reaction via intermediate RN 2 + cation was confirmed by density functional theory (DFT) calculations at the PBE0/6‐31+G(d) functional due to good agreement between calculated and experimental data on the acid stability of diazoketones in different solvents.