The di-pi-methane photorearrangement of 2,3-disubstituted benzobarrelenes and benzonorbornadiene - Substituent effects in regioselectivity

Date

2002-02-01

Author

Altundas, R
Dastan, A
Unaldi, NS
Guven, K
Uzun, O
Balcı, Metin

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2,3-Disubstituted benzobarrelene and benzonorbornadiene derivatives 16, 17, and 18, containing electron-withdrawing and electron-donating substituents, have been synthesized and subjected to triplet-sensitized photoisomerization. Methyl 3-methyl-2-benzobarrelenecarboxylate (16) gave two di-pi-methane rearrangement products. However, methyl 3-cyano-2-benzobarrelenecarboxyidte (17) underwent an intramolecular [2(pi) + 2(pi)] cycloaddition reaction, whilst methyl 3cyano-2-benzonorbornadienecarboxylate (18) formed dimer 40. The formation of these products is discussed in terms of the radical stabilizing effect of the substituents and the destabitizing effect on the formation of cyclopropane ring.

Subject Keywords

Benzobarrelene, Benzonorbornadiene, Di-pi-methane rearrangement, Photolysis

URI

https://hdl.handle.net/11511/54617

Journal

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY

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Graduate School of Natural and Applied Sciences, Article

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Citation Formats

R. Altundas, A. Dastan, N. Unaldi, K. Guven, O. Uzun, and M. Balcı, “The di-pi-methane photorearrangement of 2,3-disubstituted benzobarrelenes and benzonorbornadiene - Substituent effects in regioselectivity,” EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, pp. 526–533, 2002, Accessed: 00, 2020. [Online]. Available: https://hdl.handle.net/11511/54617.