标题：Reaction mechanism of organoselenium-catalyzed syn-dichlorination of alkenes: a DFT study
作者：Fu, Lijun; Mu, Xueli; Li, Baiqing
作者机构：[Fu, Lijun; Mu, Xueli; Li, Baiqing] Shandong Univ, Sch Chem & Chem Engn, Inst Theoret Chem, Jinan 250100, Shandong, Peoples R China.; [Fu, Lijun; Mu 更多
通讯作者：Li, BQ;Li, BQ
通讯作者地址：[Li, BQ]Shandong Univ, Sch Chem & Chem Engn, Inst Theoret Chem, Jinan 250100, Shandong, Peoples R China;[Li, BQ]Shandong Univ, Minist Educ, Key Lab Co 更多
来源：JOURNAL OF MOLECULAR MODELING
关键词：Syn-dichlorination; Diastereocontrol; Organoselenium catalyst; DFT; calculation; Reaction mechanism
摘要：A new method for the syn-dichlorination of alkenes at room temperature has been proposed by Denmark et al. The method uses diselenide (PhSeSePh) as the precatalyst, benzyltriethylammonium chloride (BnEt3NCl) as the source of chlorine, and an N-fluoropyridinium salt as the oxidant to recover the catalyst. This approach has achieved exquisite diastereocontrol on a number of alkene substrates. In this paper, we report the results of DFT calculations we performed to study the mechanism of this reaction. We were able to identify a reasonable reaction path, including the intermediate and transition-state structures. The results also indicate that PhSeCl3, rather than PhSeCl, is the active catalyst.