Balci Metin, Güney Murat, Daştan Arif, Azizoğlu Akin
Department of Chemistry, Middle East Technical University, 06531 Ankara, Turkey.
J Org Chem. 2007 Jun 22;72(13):4756-62. doi: 10.1021/jo070253b. Epub 2007 May 24.
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.
6,7,8,9-四氢-5H-5,9-亚乙基苯并[a][7]环壬烯的溴化反应生成了区域和立体特异性形成的二溴化物，这是由烷基迁移产生的，其中溴仅从双键的内表面进攻双键。对模型化合物的密度泛函理论计算表明，双键的锥形化以及亚甲基质子引起的空间排斥是溴进行立体和区域选择性加成的原因。
