Manganese(III) acetate induced cyclization of α-arylalkyl and α-(aryloxy)alkyl β-dicarbonyl derivatives

Attilio Citterio, Daniele Fancelli, Claudia Finzi, Luca Pesce, Roberto Santi

Research output: Contribution to journalArticle

Abstract

The oxidation of the title compounds by manganese(III) acetate in acetic acid at 50-80°C affords products of intramolecular aromatic alkylation. High yield and selectivity are observed in six-membered ring closures, whereas five- and seven-membered ring closures are associated with side products of dimerization and/or hydrogen abstraction. The aromatic substitution is favored in all cases by a high electron density of the aromatic carbon atom a to the carbonylalkyl substituent. The activation parameters for the oxidative cyclization of diethyl α-(2-naphthoxyethyl)malonate were determined (ΔH = 25.2 ± 0.3 kcal/mol, ΔS = 2.1 ± 0.5 cal/K mol). The reaction is interpreted to proceed through electrophilic Mn(III)-complexed β-dicarbonylalkyl radicals, formed by reversible inner-sphere electron transfer of Mn(III) carbonyl complexes, which add reversibly to the aromatic ring.

Original languageEnglish
Pages (from-to)2713-2718
Number of pages6
JournalJournal of Organic Chemistry
Volume54
Issue number11
Publication statusPublished - 1989

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Dimerization
Cyclization
Alkylation
Acetic Acid
Carrier concentration
Hydrogen
Substitution reactions
Carbon
Chemical activation
Derivatives
Atoms
Oxidation
Electrons
malonic acid
manganese(III) acetate dihydrate

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Citterio, A., Fancelli, D., Finzi, C., Pesce, L., & Santi, R. (1989). Manganese(III) acetate induced cyclization of α-arylalkyl and α-(aryloxy)alkyl β-dicarbonyl derivatives. Journal of Organic Chemistry, 54(11), 2713-2718.

Manganese(III) acetate induced cyclization of α-arylalkyl and α-(aryloxy)alkyl β-dicarbonyl derivatives. / Citterio, Attilio; Fancelli, Daniele; Finzi, Claudia; Pesce, Luca; Santi, Roberto.

In: Journal of Organic Chemistry, Vol. 54, No. 11, 1989, p. 2713-2718.

Research output: Contribution to journalArticle

Citterio, A, Fancelli, D, Finzi, C, Pesce, L & Santi, R 1989, 'Manganese(III) acetate induced cyclization of α-arylalkyl and α-(aryloxy)alkyl β-dicarbonyl derivatives', Journal of Organic Chemistry, vol. 54, no. 11, pp. 2713-2718.
Citterio, Attilio ; Fancelli, Daniele ; Finzi, Claudia ; Pesce, Luca ; Santi, Roberto. / Manganese(III) acetate induced cyclization of α-arylalkyl and α-(aryloxy)alkyl β-dicarbonyl derivatives. In: Journal of Organic Chemistry. 1989 ; Vol. 54, No. 11. pp. 2713-2718.
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AU - Pesce, Luca

AU - Santi, Roberto

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N2 - The oxidation of the title compounds by manganese(III) acetate in acetic acid at 50-80°C affords products of intramolecular aromatic alkylation. High yield and selectivity are observed in six-membered ring closures, whereas five- and seven-membered ring closures are associated with side products of dimerization and/or hydrogen abstraction. The aromatic substitution is favored in all cases by a high electron density of the aromatic carbon atom a to the carbonylalkyl substituent. The activation parameters for the oxidative cyclization of diethyl α-(2-naphthoxyethyl)malonate were determined (ΔH‡ = 25.2 ± 0.3 kcal/mol, ΔS‡ = 2.1 ± 0.5 cal/K mol). The reaction is interpreted to proceed through electrophilic Mn(III)-complexed β-dicarbonylalkyl radicals, formed by reversible inner-sphere electron transfer of Mn(III) carbonyl complexes, which add reversibly to the aromatic ring.

AB - The oxidation of the title compounds by manganese(III) acetate in acetic acid at 50-80°C affords products of intramolecular aromatic alkylation. High yield and selectivity are observed in six-membered ring closures, whereas five- and seven-membered ring closures are associated with side products of dimerization and/or hydrogen abstraction. The aromatic substitution is favored in all cases by a high electron density of the aromatic carbon atom a to the carbonylalkyl substituent. The activation parameters for the oxidative cyclization of diethyl α-(2-naphthoxyethyl)malonate were determined (ΔH‡ = 25.2 ± 0.3 kcal/mol, ΔS‡ = 2.1 ± 0.5 cal/K mol). The reaction is interpreted to proceed through electrophilic Mn(III)-complexed β-dicarbonylalkyl radicals, formed by reversible inner-sphere electron transfer of Mn(III) carbonyl complexes, which add reversibly to the aromatic ring.

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