Unusual manganese(III)-mediated oxidative free radical additions of 1,3-dicarbonyl compounds to benzonorbornadiene and 7-heterobenzonorbornadienes: Mechanistic studies

Date

2007-04-27

Author

Caliskan, Rasit
Ali, Mohamed Fadelalla
Sahin, Ertan
Watson, William H.
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

206
views

0
downloads

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 dimedone. The reaction of azanorbornadiene with 1,3-dicarbonyl compounds and Mn(OAc)3 always produced rearranged products. The mechanism of formation of the products is discussed. We generally observe that the cyclization reaction takes place after the oxidation of the initially formed radical.

Subject Keywords

Organic Chemistry

URI

https://hdl.handle.net/11511/52350

Journal

JOURNAL OF ORGANIC CHEMISTRY

DOI

https://doi.org/10.1021/jo0625711

Collections

Graduate School of Natural and Applied Sciences, Article

Suggestions

OpenMETU
Core

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...
Alkylation of l- and d-menthyl pentanoate with (20S)-20-iodomethyl-4 alpha-methyl-5 alpha-pregnane Demir, Ayhan Sıtkı (Informa UK Limited, 1996-01-01) The alkylation of l- and d-menthyl valerate with n-hexyl iodide and with (20S)-20-iodomethyl-4 alpha-methyl-5 alpha-pregnane gave modest levels of diastereoselection. The chirality of the ester group favoured slight degree of selectivity. The chiral centers had limited impact on diastereoselectivity.
ASYMMETRIC ENE REACTIONS OF 2-METHYLPROPENE WITH CHLOROALDEHYDES IN THE PRESENCE OF BORONTRIFLUORIDE-L-MENTHYLETHYL ETHERATE AKHMEDOV, IM; Tanyeli, Cihangir; AKHMEDOV, MA; MOHAMMADI, M; DEMIR, AS (Informa UK Limited, 1994-01-01) The asymmetric ene reactions of prochiral chloroaldehydes, chloral and 2,3-dichlorobutanal with 2-methylpropanal in the presence of BF3 l-menthylethyl etherate gave optically active homoallylic alcohols in 16-22% ee. The dechlorination of the chloro alcohols lead to the unsaturated derivatives of alcohols.
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...
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...

Citation Formats

R. Caliskan, M. F. Ali, E. Sahin, W. H. Watson, and M. Balcı, “Unusual manganese(III)-mediated oxidative free radical additions of 1,3-dicarbonyl compounds to benzonorbornadiene and 7-heterobenzonorbornadienes: Mechanistic studies,” JOURNAL OF ORGANIC CHEMISTRY, pp. 3353–3359, 2007, Accessed: 00, 2020. [Online]. Available: https://hdl.handle.net/11511/52350.