Electrochemical Difunctionalization of Alkenes

Abstract

The electrochemical alkene difunctionalization reaction has become a powerful and sustainable tool for the efficient construction of vicinal difunctionalized structures in organic synthesis. Since only electrons are used as the redox agents, electrochemical alkene difunctionalization avoids the need for additional redox catalysts, metal catalysts, or chemical oxidants and does not generate chemical waste. Herein we summarize the latest contributions in the electrochemical difunctionalization of alkenes over the last 3–4 years. We discuss in detail the reaction features, scopes, limitations, and mechanistic rationalizations of three categories of alkene difunctionalization methods: (1) electrochemical alkene difunctionalization terminated by nucleophiles, (2) electrochemical difunctionalization of alkenes terminated by radicals, and (3) electrochemical alkene difunctionalization terminated by functionality migration.

Iron-Catalyzed Regioselective Reductive Fluoroalkylalkenylation of Unactivated Alkenes

“…After establishing the optimized reaction conditions, our focus shifted to the comprehensive exploration of the scope of the reductive fluoroalkylalkenylation of unactivated alkenes. As illustrated in Table 2, the method demonstrated remarkable tolerance toward various functional groups, including MeS, fluoro, chloro, bromo, OCF 3 , SCF 3 , CF 3 , CN, carboxylate, sulfone, Bpin, alkenyl, TMS, SiMe 2 Ph, iodo, OTBS, alkynyl, and TIPS (1,12,13,14,15,16,17,18,19,20,21,26,28,29,35,37,46,47). Moreover, this reaction exhibited excellent compatibility with alkenyl bromides, alkenes, and fluoroalkyl bromides.…”

“…Transition metal-catalyzed difunctionalization of alkenes has been proven as an effective method for rapidly achieving molecular complexity through the simultaneous construction of two vicinal carbon–carbon bonds. − However, the unsatisfactory regioselectivity of the newly formed two carbon–carbon bonds often hinders their broad applications in organic synthesis, especially in the case of unactivated alkenes. This difficulty can be attributed to the weak resonance effects of in situ generated alkyl radicals, which tend to be highly reactive and can lead to many unwanted side reactions.…”

Electrode-switchable: exploring this new strategy to achieve regiodivergent azidoiodination of alkenes

“…The functionalization of alkenes is an efficient strategy for constructing economic or applied valueadded structurally complicated organic molecules by implanting two substituents in one step. 1 To date, the regiodivergent functionalization of alkenes has received significant attention because of its synthetic practicality. This involves controlling the regiochemistry of the CvC bond via Markovnikov and anti-Markovnikov's processes to form regioisomers from the same starting reactant, and many effective systems have been established for those transformations using transition-metal catalysts.…”

Electrochemical Organic Synthesis

“…2 Qin, Li and co-workers present an indepth review of electrochemical difunctionalization of alkenes. 3 Lu and his team delve into transition-metal electrochemical asymmetric catalysis including the recently emerged photoelectrochemical asymmetric catalysis (PEAC). 4 Phillips, Pombeiro, and associates encapsulate the power of electrochemistry in catalytic enantioselective synthesis.…”