Unusual oxidative free-radical additions of 1,3-dicarbonyl compounds to benzonorbornadiene and oxabenzonorbornadiene

Date

2005-09-12

Author

Cahskan, R
Pekel, T
Watson, WH
Balcı, Metin

Metadata

Show full item record

This work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License.

Item Usage Stats

138
views

0
downloads

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 mechanism of formation of the products is discussed.

Subject Keywords

Organic Chemistry, Biochemistry, Drug Discovery

URI

https://hdl.handle.net/11511/50637

Journal

TETRAHEDRON LETTERS

DOI

https://doi.org/10.1016/j.tetlet.2005.07.051

Collections

Graduate School of Natural and Applied Sciences, Article

Suggestions

OpenMETU
Core

Unusual manganese(III)-mediated oxidative free-radical additions of Meldrum's acid and dimethyl malonate to benzonorbornadiene and oxabenzonorbornadiene ÇALIŞKAN, Raşit; Nohut, Neslihan; Yilimaz, Ozlem; ŞAHİN, Ertan; Balcı, Metin (Elsevier BV, 2017-01-26) 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 malo...
Unusual manganese(III)-mediated oxidative free radical additions of 1,3-dicarbonyl compounds to benzonorbornadiene and 7-heterobenzonorbornadienes: Mechanistic studies Caliskan, Rasit; Ali, Mohamed Fadelalla; Sahin, Ertan; Watson, William H.; Balcı, Metin (American Chemical Society (ACS), 2007-04-27) Benzonorbornadiene and heterobenzonorbornadiene were reacted with dimedone/acetylacetone and Mn(OAc)3 in the presence and absence of Cu(OAc)2. The reaction of benzonorbornadiene with dimedone gave mainly the dihydrofuran addition product, whereas the reaction with acetylacetone produced a rearranged product in addition to the dihydrofuran derivative. On the other hand, oxanorbornadiene gave unusual products such as the cycloproponated compound and a product arising from the incorporation of 2 mol of dimedon...
Manganese(III)-mediated oxidative free-radical additions of 1,3-dicarbonyl compounds to homobenzonorbornadiene and benzobarrelene: mechanistic studies Ali, Mohamed Fadelalla; Caliskan, Rasit Ali; ŞAHİN, Ertan; Balcı, Metin (Elsevier BV, 2009-02-14) 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...
The chemistry of homophthalic acid: a new synthetic strategy for construction of substituted isocoumarin and indole skeletons Oezcan, Sevil; Balcı, Metin (Elsevier BV, 2008-06-02) Homophthalic acid was reacted with thionylchloride/DMF and chloroethylformate/NEt(3) in the presence and absence of NaN(3). in all cases completely different isocoumarin derivatives were obtained. These unusual isocoumarin derivatives were isolated and characterized and their formation mechanisms are discussed. The homophthalic acid monomethyl ester was converted into the corresponding isocyanate. Reaction of the isocyanate with different amines produced the urea derivatives. Base-supported condensation rea...
Highly efficient and selective olefination of acyl phosphonates with ethyl diazoacetate catalyzed by a cobalt(II) porphyrin complex Erturk, Erkan; Demir, Ayhan Sıtkı (Elsevier BV, 2008-08-04) The cobalt(II) porphyrin complex (CoTPP) was found to be an efficient catalyst for the Wittig type olefination of acyl phosphonates with ethyl diazoacetate (EDA) in the presence of triphenylphosphine (Ph(3)P). By using this one pot methodology under mild conditions, densely functionalized vinyl phosphonates were obtained in high yields and high E/Z selectivities in relatively short reaction times. A rather broad substrate spectrum and steric influence on the reaction rate were observed.

Citation Formats

R. Cahskan, T. Pekel, W. Watson, and M. Balcı, “Unusual oxidative free-radical additions of 1,3-dicarbonyl compounds to benzonorbornadiene and oxabenzonorbornadiene,” TETRAHEDRON LETTERS, pp. 6227–6230, 2005, Accessed: 00, 2020. [Online]. Available: https://hdl.handle.net/11511/50637.