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

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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

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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.