Publication

Iron-Catalyzed Reductive Coupling of Alkyl Iodides with Alkynes To Yield cis-Olefins: Mechanistic Insights from Computation

Xile Hu
2020
Journal paper

Abstract

In a recent study, a new procedure for Z-selective olefin synthesis by reductive coupling of alkyl iodides with terminal alkynes in the presence of iron salts is described. This transformation is representative of many newly developed synthetic routes through the involvement of multiple species and phases, which makes mechanistic insight hard to obtain. Here, we report computational work aimed at exploring the possible reaction pathways. DFT calculations lead to two suggested routes, one involving C-I reduction by metallic zinc and radical addition to the alkyne and the other involving addition of two reduced iron species to the alkyne bond followed by reductive elimination. Comparison to experimental results as well as kinetic modeling is used to discuss the likelihood of these and related mechanisms.

Official source

https://infoscience.epfl.ch/record/275690?ln=en

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Ontological neighbourhood

Chemistry

Organic chemistry: Organometallic chemistry

Related concepts (34)

In organic chemistry, the Kumada coupling is a type of cross coupling reaction, useful for generating carbon–carbon bonds by the reaction of a Grignard reagent and an organic halide. The procedure uses transition metal catalysts, typically nickel or palladium, to couple a combination of two alkyl, aryl or vinyl groups. The groups of Robert Corriu and Makoto Kumada reported the reaction independently in 1972. The reaction is notable for being among the first reported catalytic cross-coupling methods.

In organic chemistry, a cross-coupling reaction is a reaction where two different fragments are joined. Cross-couplings are a subset of the more general coupling reactions. Often cross-coupling reactions require metal catalysts. One important reaction type is this: (R, R' = organic fragments, usually aryle; M = main group center such as Li or MgX; X = halide) These reactions are used to form carbon–carbon bonds but also carbon-heteroatom bonds. Cross-coupling reaction are a subset of coupling reactions.

Acetylene Propyne 1-Butyne In organic chemistry, an alkyne is an unsaturated hydrocarbon containing at least one carbon—carbon triple bond. The simplest acyclic alkynes with only one triple bond and no other functional groups form a homologous series with the general chemical formula . Alkynes are traditionally known as acetylenes, although the name acetylene also refers specifically to , known formally as ethyne using IUPAC nomenclature. Like other hydrocarbons, alkynes are generally hydrophobic.

Related publications (65)

Related MOOCs (1)

Iron-Catalyzed Reductive Coupling of Alkyl Iodides with Alkynes To Yield cis-Olefins: Mechanistic Insights from Computation

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