7150-12-1Relevant articles and documents
Nickel-Catalyzed Reductive Carboxylation of Cyclopropyl Motifs with Carbon Dioxide
Moragas, Toni,Martin, Ruben
, p. 2816 - 2822 (2016/08/26)
A nickel-catalyzed reductive carboxylation technique for the synthesis of cyclopropanecarboxylic acids has been developed. This user-friendly and mild transformation operates at atmospheric pressure of carbon dioxide and utilizes either organic halides or alkene precursors, thus representing the first example of catalytic reductive carboxylation of secondary counterparts lacking adjacent π-components.
Diazodiphenylmethane and monosubstituted butadienes: Kinetics and a new chapter of vinylcyclopropane chemistry
Ohta, Akihiro,Dahl, Klaus,Raab, Rainer,Geittner, Jochen,Huisgen, Rolf
experimental part, p. 783 - 804 (2009/03/11)
Diazodiphenylmethane (DDM) undergoes cycloadditions to 1-substituted buta-1,3-dienes exclusively at the C(3)=C(4) bond. At room temperature, the N2 loss from the initially formed 4,5-dihydro-3H-pyrazoles 2 is faster than the cycloaddition and furnishes the vinylcyclopropane derivatives 7 and 9 with structural retention at the C(1)=C(2) bond. 2-Substituted butadienes react with DDM at the C(3)=C(4) bond to give 12; isoprene, however, affords 3,4/1,2 products in the ratio of 86:14. DDM is a nucleophilic 1,3-dipole: 1-Cyanobutadiene reacts 400 times faster than 1-methoxybuta-1,3-diene (DMF, 40°). The log k2 for the additions to six 1-substituted butadienes show a linear correlation with σp (Hammett) and ρ = +2.9; the log k2 of five 2-substituted butadienes are linearly related to Taft's σI (ρ = +1.7). The structures of the vinylcyclopropanes 7, 9, and 12 are established by NMR spectra and oxidation. A cyclopropyl carbinyl cation is made responsible for the isomerization of 12, R = Ph, Me, by acetic acid to 4-substituted 1,1-diphenylpenta-1,3-dienes 25 and 29; TsOH at 200° converts 25 further to 9,10-dihydro-9-methyl-10-phenyl-9,10-ethanoanthracene (27). Thermal rearrangement of 7, 9, and 12 at 200-300° produces the 3- or 1-substituted 4,4-diphenylcyclopentenes 30 and 31. These give the same mass spectra as the vinylcyclopropanes, and an open-chain distonic radical cation is suggested as common intermediate. Besides spectroscopic evidence for the cyclopentene structures, hydrogenation and epoxidation are described; NMR data support the trans-attack by perbenzoic acid.
Facile synthesis of substituted trans-2-arylcyclopropylamine inhibitors of the human histone demethylase LSD1 and monoamine oxidases A and B
Gooden, David M.,Schmidt, Dawn M.Z.,Pollock, Julie A.,Kabadi, Ami M.,McCafferty, Dewey G.
, p. 3047 - 3051 (2008/12/23)
A facile synthetic route to substituted trans-2-arylcyclopropylamines was developed to provide access to mechanism-based inhibitors of the human flavoenzyme oxidase lysine-specific histone demethylase LSD1 and related enzyme family members such as monoamine oxidases A and B.
