35673-05-3Relevant articles and documents
Merging shuttle reactions and paired electrolysis for reversible vicinal dihalogenations
Dong, Xichang,Roeckl, Johannes L.,Waldvogel, Siegfried R.,Morandi, Bill
, (2021/02/12)
Vicinal dibromides and dichlorides are important commodity chemicals and indispensable synthetic intermediates in modern chemistry that are traditionally synthesized using hazardous elemental chlorine and bromine. Meanwhile, the environmental persistence of halogenated pollutants necessitates improved approaches to accelerate their remediation. Here, we introduce an electrochemically assisted shuttle (e-shuttle) paradigm for the facile and scalable interconversion of alkenes and vicinal dihalides, a class of reactions that can be used both to synthesize useful dihalogenated molecules from simple alkenes and to recycle waste material through retro-dihalogenation. The reaction is demonstrated using 1,2-dibromoethane, as well as 1,1,1,2-tetrachloroethane or 1,2-dichloroethane, to dibrominate or dichlorinate, respectively, a wide range of alkenes in a simple setup with inexpensive graphite electrodes. Conversely, the hexachlorinated persistent pollutant lindane could be fully dechlorinated to benzene in soil samples using simple alkene acceptors.
Electrocatalytic Radical Dichlorination of Alkenes with Nucleophilic Chlorine Sources
Fu, Niankai,Sauer, Gregory S.,Lin, Song
supporting information, p. 15548 - 15553 (2017/11/06)
We report a Mn-catalyzed electrochemical dichlorination of alkenes with MgCl2 as the chlorine source. This method provides operationally simple, sustainable, and efficient access to a variety of vicinally dichlorinated compounds. In particular, alkenes with oxidatively labile functional groups, such as alcohols, aldehydes, sulfides, and amines, were transformed into the desired vicinal dichlorides with high chemoselectivity. Mechanistic data are consistent with metal-mediated Cl atom transfer as the predominant pathway enabling dual C-Cl bond formation and contradict an alternative pathway involving electrochemical evolution of chlorine gas followed by Cl2-mediated electrophilic dichlorination.
Vicinal dichlorination of olefins using NH4Cl and oxone
Swamy, Peraka,Reddy, Marri Mahender,Kumar, Macharla Arun,Naresh, Mameda,Narender, Nama
, p. 251 - 257 (2014/03/21)
A mild and efficient protocol for the preparation of 1,2-dichloroalkane derivatives from olefins using NH4Cl and Oxone at room temperature is described. A variety of terminal, internal, and cyclic alkenes reacted smoothly to give the corresponding dichlorinated products in good to excellent yields. Moreover, 1,2-disubstituted symmetrical and unsymmetrical olefins dichlorinated with moderate to excellent diastereoselectivity. This method precludes the use of acidic additives and transition metals in the synthesis of vicinal dichlorides.
