The effect of the double bond pyramidalization on the mode of the bromination reaction: Bromination of benzobicyclononadiene

Date

2007-06-22

Author

Balcı, Metin
Guney, Murat
Dastan, Arif
Azizoglu, Akin

Metadata

Show full item record

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

Item Usage Stats

56
views

0
downloads

The bromination of 6,7,8,9-tetrahydro-5H-5,9-ethenobenzo[a][7]annulene yielded regio- and stereospecifically formed dibromides arising from the alkyl shift where the bromine exclusively attacks the double bond from the endo face of the double bond. DFT calculations on model compounds showed that the pyramidalization of the double bond and steric repulsion caused by the methylene protons are responsible for the stereo- and regioselective addition of bromine.

Subject Keywords

Organic Chemistry

URI

https://hdl.handle.net/11511/57862

Journal

JOURNAL OF ORGANIC CHEMISTRY

DOI

https://doi.org/10.1021/jo070253b

Collections

Graduate School of Natural and Applied Sciences, Article

Suggestions

OpenMETU
Core

A facile synthesis of various butenolides Tanyeli, Cihangir (Informa UK Limited, 2000-01-01) The synthesis of alpha'-acyloxy-alpha,beta-unsaturated cyclic ketones from the corresponding alpha,beta-unsaturated cyclic ketones by using manganese (III) acetate in combination with 2-chloropropionic acid followed by subsequent Arbuzov and intramolecular Horner-Emmons cyclization reactions provided a convenient synthetic pathway to various butenolides 4a-d.
One-pot synthesis of chloroalcohols and their lipase mediated kinetic resolution - ferrocenyl aziridinylmethanols as chiral ligands in enantioselective conjugate diethylzinc addition to enones İşleyen, Alper; Doğan, Özdemir; Department of Chemistry (2007) An unexpected tricyclic ether formation instead of acetate addition to the double bond of a norbornene derivative aroused our interest to explore the mechanism of this reaction. Mechanistic studies showed that methylene diacetate (MDA) was formed in the stock solution (NBu4OAc + dichloromethane) and decomposed to formaldehyde under Lewis or Brønsted acid conditions. Formaldehyde and olefin condensation (Prins reaction) clearly explains the formation of the unexpected product. Same methodology was then succe...
AN EFFICIENT SYNTHESIS OF SUBSTITUTED 2H-PYRAN-2-ONE DERIVATIVES VIA THE CONJUGATED ADDITION OF THE ENOLATES OF CARBONYL-COMPOUNDS TO ENAMINOESTERS DEMIR, AS; Tanyeli, Cihangir; URKMEZKARAASLAN, R; SAYRAC, T (Informa UK Limited, 1991-01-01) Short simple synthesis of alkenoic acid esters and their intramolecular cyclization products, 2H-Pyran-2-ones from enolates of carbonyl compounds and enaminoesters are described.
THE ALPHA'-OXIDATION OF ALPHA-ALKOXY ENONES USING MANGANESE(III) ACETATE IN COMBINATION WITH CARBOXYLIC-ACIDS Demir, Ayhan Sıtkı; SAATCIOGLU, A (Informa UK Limited, 1993-01-01) The alpha'-oxidation of cyclic derivatives of alpha-alkoxy-alpha,beta-unsaturated ketones using manganese(III)acetate in the presence of various carboxylic acids provided a convenient synthesis of 5-acyloxy-2-alkoxy-2-cyclopentenones and 6-acyloxy-2-alkoxy-2-cyclohexenones.
Synthesis of 1,2,3,5- tetrasubstituted pyrrole derivatives via 5-exo-dig type cyclization and stereoselective functionalisation of ferrocene derivatives Kayalar, Metin; Demir, Ayhan Sıtkı; Department of Chemistry (2005) A convenient and new method for the synthesis of 1,2,3,5-tetrasubstituted pyrrole derivatives starting from 1,3,-dicarbonyl compounds through acid catalyzed cyclization reaction is described. Alkylation of 1,3-dicarbonyl compound with propargyl bromide followed by one step cyclization with the introduction of primary amines in the presence of catalytic amount of triflouroacetic acid (TFA) affords the corresponding pyrrole derivatives in high yields. The investigations on the studies of developing a new meth...

Citation Formats

M. Balcı, M. Guney, A. Dastan, and A. Azizoglu, “The effect of the double bond pyramidalization on the mode of the bromination reaction: Bromination of benzobicyclononadiene,” JOURNAL OF ORGANIC CHEMISTRY, pp. 4756–4762, 2007, Accessed: 00, 2020. [Online]. Available: https://hdl.handle.net/11511/57862.