103670-60-6Relevant articles and documents
Microwave-Assisted Dibromoolefination of Aromatic and Heteroaromatic Aldehydes and Ketones
Nauroozi, Djawed,Bruhn, Clemens,Fürmeier, Sven,Holzhauer, J?rn-Uwe,Faust, Rüdiger
, p. 615 - 619 (2016)
Microwave (MW) irradiation was successfully employed to convert aromatic and heteroaromatic aldehydes and ketones efficiently to the corresponding dibromoolefins. Exemplified by the successful dibromoolefination of traditionally inert pyridyl-flanked carbonyls, MW activation significantly broadens the scope of this valuable transformation, although some limitations especially with electron-rich aromatic ketone derivatives remain.
Ruthenium catalyzed reductive coupling of paraformaldehyde to trifluoromethyl allenes: CF3-bearing all-carbon quaternary centers
Sam, Brannon,Montgomery, T. Patrick,Krische, Michael J.
supporting information, p. 3790 - 3793 (2013/08/23)
Trifluoromethyl substituted allenes engage in ruthenium catalyzed reductive couplings with paraformaldehyde to form products of hydrohydroxymethylation as single regioisomers. This method enables generation of CF3-bearing all-carbon quaternary
Re-investigation of the coupling reaction of 2-aryl-1,1-dibromo-3,3,3- trifluoropropenes. Preparation of perfluoroalkylated [3]cumulenes
Uno, Hidemitsu,Nibu, Nobumasa,Misobe, Noboru
, p. 1365 - 1375 (2007/10/03)
The coupling reaction of perfluoroalkylated 2-aryl-1,1-dibromoalkenes using zinc and copper(1) bromide gave stereoisomeric mixtures of [3]cumulenes and [4]radialenes. The ratio of [3]cumulenes and [4]radialenes mainly depended upon the reaction temperature and the electronic character of the aryl group. When the coupling reaction was carried out at -40 °C, (E)- and (Z)-[3]cumulenes were obtained in good selectivity and only trace amounts of [4]radialenes were detected by a 19FNMR analysis. On the other hand, a similar reaction at -60 °C afforded a considerable amount of [4]radialene isomers. When the cis-[3]cumulenes were heated at an appropriate temperature, selective isomerization to trans-[3]cumulenes occurred.
Synthesis of fluorinated 1,2,3-butatrienes from α-halovinyl organometallic reagents
Morken,Bachand, Patrick C.,Swenson, Dale C.,Burton, Donald J.
, p. 5430 - 5439 (2007/10/02)
The thermal stability and dimerization reaction of fluorinated α-halovinyl zinc and copper reagents, RR'C=CYM (Y = F, Cl, Br; M = ZnX, Cu), have been explored in detail. Dimerization of these vinyl carbenoids to betatrienes occurred when R was an aromatic (C6H5 or C6F5) and R' was a perfluoroalkyl group (CF3, C2F5, C3F7). The role of the α-halogen was determined; the α-F vinyl copper reagent (R = C6H5, R' = CF3) decomposed by oxidative dimerization to 1,3-dienes while the α-Br and -Cl copper reagents dimerized to butatrienes. The fluorinated butatrienes prepared in this study, (E)- and (Z)-R1R2C==C=C=CR1R2 (R1 = CF3, R2 = C6H5; R1 = C2F5, R2 = C6H5; R1 = n-C3F7, R2 = C6H5; R1 = CF3, R2 = C6F5) are available on a multigram scale and readily obtained with high isomeric purity. The geometry of one member of each isomeric pair of butatrienes was characterized by X-ray crystallography. The mechanism of the dimerization reaction has been determined to be a nucleophilic displacement/β-elimination process. Diels-Alder (1,2-addition), bromination (1,2-addition), and isomerizatioa reactions are described.
Butatriene Formation via CuBr-induced Self Coupling of an α-Bromo Vinyl Zinc Reagent: Synthesis and X-Ray Structure of Z-1,1,1,6,6,6-Hexafluoro-2,5-diphenylhexa-2,3,4-triene
Morken, Peter A.,Baenziger, Norman C.,Burton, Donald J.,Bachand, Patrick C.,Davis, Charles R.,et al.
, p. 566 - 567 (2007/10/02)
Title cumulenes 2a and 2b were prepared by reaction of CF3(Ph)C=C(Br)ZnX 1 with CuBr, or by oxidative coupling of 1 with FeCl3 to form 2a,b and 2 3, which can be dehalogenated with zinc to afford 2a,b; the cumulene isomers are readily separated by silica-gel chromatography, and may be prepared in good yield on a multi-gram scale.
