Unusual manganese(III)-mediated oxidative free-radical additions of Meldrum's acid and dimethyl malonate to benzonorbornadiene and oxabenzonorbornadiene

Nohut, Neslihan
Yilimaz, Ozlem
ŞAHİN, Ertan
Balcı, Metin
Benzonorbornadiene and 7-oxabenzonorbornadiene were reacted with Meldrum's acid and dimethyl malonate in the presence of Mn(OAc)(3) and Cu(OAc)(2) in acetic acid. The reaction of benzonorbornadiene with Meldrum's acid gave a naphthalene derivative whereas the reaction with dimethyl malonate formed rearranged products derived from a carbocation intermediate. However, the reaction of 7-oxabenzonorbornadiene with Meldrum's acid gave two nonrearranged products. On the other hand, the reaction with dimethyl malonate unexpectedly formed a dihydronapthalene derivative with an unusual structure. The mechanism for the formation of the products is discussed.


Unusual oxidative free-radical additions of 1,3-dicarbonyl compounds to benzonorbornadiene and oxabenzonorbornadiene
Cahskan, R; Pekel, T; Watson, WH; Balcı, Metin (Elsevier BV, 2005-09-12)
Benzonorbornadiene and oxabenzonorbornadiene were reacted with dimedone and acetylacetone in the presence of Mn(OAc)(3) and Cu(OAc)(2). The reaction of benzonorbornadiene with dimedone gave the dihydrofuran addition product, whereas the reaction with acetylacetone produced, in addition to the dihydrofuran derivative, a rearranged product. On the other hand, oxanorbornadiene gave unusual products such as the cyclopropanated compound and the product arising from the addition of two moles of dimedone. The mech...
Manganese(III)-mediated oxidative free-radical additions of 1,3-dicarbonyl compounds to homobenzonorbornadiene and benzobarrelene: mechanistic studies
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Homobenzonorbornadiene and benzobarrelene were reacted with dimedone/acetylacetone and Mn(OAc)(3) in the presence of Cu(OAc)(2) in acetic acid. Mainly rearranged products having a [2.2.2]skeleton and the nonrearranged dihydrofuran derivatives were obtained. These observations clearly indicated that the second oxidation takes place before the cyclization reaction. Furthermore, intramolecular tandem oxidations were observed where unusually oxyl radicals attack the double bond to form the products. The mechani...
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Homophthalic acid was reacted with thionyl chloride/DMF and ethyl chloroformate/NEt3 in the presence and absence of NaN3. In all cases completely different isocoumarin derivatives were obtained. These unusual isocournarin derivatives were characterized and their mechanism of formation is discussed.
Efficient rearrangement of epoxides catalyzed by a mixed-valent iron trifluoroacetate [Fe3O(O2CCF3)(6)(H2O)(3)]
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The mixed-valent oxo-centered triiron(III, III, II) trifluoroacetate complex [(Fe2FeO)-Fe-III-O-II(C2CCF3)(6)(H2O)(3)] Was prepared by reacting anhydrous iron(III) chloride with boiling trifluoroaceric acid under nitrogen. The non-hygroscopic and readily available mixed-valent triiron trifluoroacetate complex Was found to be an efficient catalyst for the regioselective rearrangement of epoxides. A number of carbonyl compounds formed via the rearrangement of epoxides could be obtained by a simple filtration ...
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Demir, Ayhan Sıtkı; Reis, O; Igdir, AC (Elsevier BV, 2004-04-05)
Mn(OAc)(3) mediated alpha'-acetoxylation of alpha,beta-unsaturated enones is reinvestigated from a synthetic and mechanistic point of view and an improved procedure based on the use of acetic acid as a co-solvent is presented. Excellent results were obtained for a variety of structurally diverse and synthetically important enones under the optimized conditions.
Citation Formats
R. ÇALIŞKAN, N. Nohut, O. Yilimaz, E. ŞAHİN, and M. Balcı, “Unusual manganese(III)-mediated oxidative free-radical additions of Meldrum’s acid and dimethyl malonate to benzonorbornadiene and oxabenzonorbornadiene,” TETRAHEDRON, pp. 291–297, 2017, Accessed: 00, 2020. [Online]. Available: https://hdl.handle.net/11511/56733.