1332928-54-7Relevant articles and documents
Three-Component Chlorophosphinoylation of Alkenes via Anodically Coupled Electrolysis
Fu, Niankai,Lin, Song,Lu, Lingxiang
, p. 1199 - 1203 (2019)
We report the development of an electrocatalytic protocol for the chlorophosphinoylation of simple alkenes. Driven by electricity and mediated by a Mn catalyst, the heterodifunctionalization reaction takes place with high efficiency and regioselectivity. Cyclic voltammetry data are consistent with a mechanistic scenario based on anodically coupled electrolysis in which the generation of two distinct radical intermediates occur simultaneously on the anode and are both mediated by the Mn catalyst.
Mn-Catalyzed Electrochemical Chloroalkylation of Alkenes
Fu, Niankai,Shen, Yifan,Allen, Anthony R.,Song, Lu,Ozaki, Atsushi,Lin, Song
, p. 746 - 754 (2019/01/11)
The heterodifunctionalization of alkenes is an efficient method for synthesizing highly functionalized organic molecules. In this report, we describe the use of anodically coupled electrolysis for the catalytic chloroalkylation of alkenes - a reaction that constructs vicinal C-C and C-Cl bonds in a single synthetic operation - from malononitriles or cyanoacetates and NaCl. Knowledge of the persistent radical effect guided the reaction design and development. A series of controlled experiments, including divided-cell electrolysis that compartmentalized the anodic and cathodic events, allowed us to identify the key radical intermediates and the pathway to their electrocatalytic formation. Cyclic voltammetry data further support the proposed mechanism entailing the parallel, Mn-mediated generation of two radical intermediates in an anodically coupled electrolysis followed by their selective addition to the alkene.
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.
