60983-24-6Relevant academic research and scientific papers
Iridium-Catalyzed Alkene-Selective Transfer Hydrogenation with 1,4-Dioxane as Hydrogen Donor
Zhang, Deliang,Iwai, Tomohiro,Sawamura, Masaya
supporting information, p. 5867 - 5872 (2019/08/26)
The iridium-catalyzed transfer hydrogenation of alkenes using 1,4-dioxane as a hydrogen donor is described. The use of 1,2-bis(dicyclohexylphosphino)ethane (DCyPE), featuring bulky and highly electron-donating properties, led to high catalytic activity. A polystyrene-cross-linking bisphosphine PS-DPPBz produced a reusable heterogeneous catalyst. These homogeneous and heterogeneous protocols achieved chemoselective transfer hydrogenation of alkenes over other potentially reducible functional groups such as carbonyl, nitro, cyano, and imino groups in the same molecule.
Formation of quaternary centers by copper-catalyzed asymmetric conjugate addition of alkylzirconium reagents
Sidera, Mireia,Roth, Philippe M. C.,Maksymowicz, Rebecca M.,Fletcher, Stephen P.
supporting information, p. 7995 - 7999 (2013/08/23)
Pure and simple: Alkylzirconocenes generated in situ from simple alkenes are used in highly enantioselective copper-catalyzed 1,4-addition reactions to trisubstituted cyclic enones to generate quaternary centers. These reactions operate at room temperature under a range of conditions and tolerate many functional groups. Cp=cyclopentadienyl, Tf=trifluoromethanesulfonyl. Copyright
Copper-catalyzed asymmetric conjugate addition of aryl aluminum reagents to trisubstituted enones: Construction of aryl-substituted quaternary centers
Hawner, Christine,Li, Kangying,Cirriez, Virginie,Alexakis, Alexandre
supporting information; experimental part, p. 8211 - 8214 (2009/04/13)
(Chemical Equation Presented) Al be back: Novel aryl and alkenyl aluminum reagents are generated through a halogen/Li exchange-Li/Al transmetalation sequence. These aryl alanes are used in the copper-catalyzed asymmetric conjugate addition reaction to a variety of cyclic enones giving chiral aryl-substituted quaternary centers (see scheme). Both, electron-donating and electron-withdrawing groups give full conversion and very good ee values.
Regioselective radical ring-opening reaction of bicyclo[4.2.0]octan-2-ones promoted by samarium(II) iodide
Kakiuchi, Kiyomi,Minato, Koichi,Tsutsumi, Ken,Morimoto, Tsumoru,Kurosawa, Hideo
, p. 1963 - 1966 (2007/10/03)
Radical ring-opening reactions of bicyclo[4.2.0]octanones, its C6 alkyl derivatives, and tricyclic ketones promoted by SmI2 gave cyclohexanones via fission of the external cyclobutane bond. The CO2Me, CN, and phenyl derivatives led t
1,4-Addition of diorganozincs to α,β-unsaturated ketones catalyzed by a copper(I)-sulfonamide combined system
Kitamura, Masato,Miki, Takashi,Nakano, Keiji,Noyori, Ryoji
, p. 999 - 1014 (2007/10/03)
A mixture of CuCN and N-benzylbenzenesulfonamide catalyzes the 1,4- addition of dialkylzincs or diarylzincs (Cu: Zn = 1: 200 to 1: 10000) to α,β-unsaturated ketones to give, after aqueous workup, the corresponding β-substituted ketones in nearly quantitative yields. A range of cyclic enones having s-cis or s-trans geometries as well as conformationally flexible acyclic enones are usable as substrates. The ethyl group migrates more readily than the methyl and phenyl groups. CuOTf, CuO-t-C4H9, and mesitylcopper can be used in place of CuCN. The in situ-formed alkylzinc enolate, prior to aqueous workup, further undergoes an aldol reaction with aldehydes or Pd(0)-assisted coupling with allyl acetate, resulting in regio- controlled, vicinal carbacondensation products. A catalytic cycle is proposed on the basis of a kinetic study and a structural analysis of the zinc enolate product by NMR and molecular weight measurements.
Alkylating agent and 1,4-addition process of an alkyl group onto an α,β-unsaturated ketone compound
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, (2008/06/13)
Disclosed is an alkylating agent that contains an aluminum reagent Alk3-m AlLm, in which Alk means a methyl, ethyl, n- or i-propyl, n-, i- or tert-butyl, pentyl, hexyl, heptyl or octyl group, which all can also be branched, L means an ethoxy group, a chlorine or bromine atom, and m is equal to 1 or 2, as an alkyl source or else zinc dimethyl as a methyl source, which contains in addition catalytic amounts of one or more copper(I) and/or copper(II) compounds and one (or more) silyl reagent(s) of general formula III in which R1, R2 and R3 are as defined herein, as well as a process for 1,4-addition of an alkyl group to an α,β-unsaturated ketone or an α,β-double unsaturated ketone or to an α,β-unsaturated aldehyde with use of the agent according to the invention. The alkylating agent yields biologically active compounds in excellent yields and the new alkylating agent/process is distinguished by its environmental compatibility based on a CKW (chlorinated hydrocarbon)-free reaction medium.
