52921-98-9Relevant academic research and scientific papers
Selective functionalization of a variety of hydrocarbon c(sp3)-h bonds initiated by Cp?W(NO)(CH2CMe3)(η3-CH2CHCHPh)
Wakeham, Russell J.,Baillie, Rhett A.,Patrick, Brian O.,Legzdins, Peter,Rosenfeld, Devon C.
, p. 39 - 52 (2017/04/04)
Cp?W(NO)(CH2CMe3)(η3-CH2CHCHPh) (1) effects C(sp3)-H activations of methane, ethane, propane, and n-butane exclusively at their terminal carbons and forms the corresponding Cp?W(NO)(alkyl)(η3-CH2- CHCHPh) complexes. It also activates (n-Bu)2O, 1-chloropropane, and Me4Si in a similar manner. Exposure of the Cp?W(NO)(alkyl)(η3-CH2CHCHPh) complexes to carbon monoxide results in initial 1,1-CO insertion into the newly formed tungsten-alkyl bonds and formation of the corresponding η1-acyl complexes, some of which can be isolated. Additional functionalization of the C-H activation products occurs upon exposure to CO under more forcing conditions. Such treatment produces η2-bound unsaturated-ketone complexes resulting from CO insertion into the W-alkyl σ bonds followed by cross-coupling of the η1-acyl and the η3-allyl ligands and coordination of CO at the resulting vacant coordination site at tungsten. The unsaturated ketones can be released from the metal's coordination spheres either by photolysis of the complexes in MeCN or by further exposure of them to CO. All new compounds have been characterized by conventional spectroscopic and analytical methods, and the solid-state molecular structures of six of them have been established by single-crystal X-ray crystallographic analyses.
Nickel-catalyzed electrochemical couplings of vinyl halides: Synthetic and stereochemical aspects
Cannes,Condon,Durandetti,Perichon,Nedelec
, p. 4575 - 4583 (2007/10/03)
Homo- and cross-coupling involving alkenyl halides have been performed efficiently using an electroassisted nickel-complex catalysis. Valuable product such as conjugated dienes, β,γ- or γ,δunsaturated esters, ketones, or nitriles, as well as alkenylated aryl compounds are thus prepared with high yields and high stereoselectivity. Partial isomerization is only observed in a few cases, when the alkenyl halide is involved in a late step of the catalytic cycle. This is the case in the preparation of (Z,Z)-1,3-diene.
