28523-15-1Relevant academic research and scientific papers
Mild Iridium-Catalysed Isomerization of Epoxides. Computational Insights and Application to the Synthesis of β-Alkyl Amines
Cabré, Albert,Cabezas-Giménez, Juanjo,Sciortino, Giuseppe,Ujaque, Gregori,Verdaguer, Xavier,Lledós, Agustí,Riera, Antoni
supporting information, p. 3624 - 3631 (2019/07/10)
The isomerization of epoxides to aldehydes using the readily available Crabtree's reagent is described. The aldehydes were transformed into synthetically useful amines by a one-pot reductive amination using pyrrolidine as imine-formation catalyst. The reactions worked with low catalyst loadings in very mild conditions. The procedure is operationally simple and tolerates a wide range of functional groups. A DFT study of its mechanism is presented showing that the isomerization takes place via an iridium hydride mechanism with a low energy barrier, in agreement with the mild reaction conditions. (Figure presented.).
Regioselective and stereoselective entry to β,β-disubstituted vinyl ethers via the sequential hydroboration/Suzuki-Miyaura coupling of ynol ethers
Cui, Weijian,Mao, Mengyi,He, Zuying,Zhu, Gangguo
, p. 9815 - 9821 (2013/10/22)
A highly regio- and stereoselective synthesis of stereodefined β,β-disubstituted alkenyl ethers featuring the sequential hydroboration/Suzuki-Miyaura coupling of ynol ethers has been described. A number of functional groups, including OMe, Ac, CO2Et, CN, halides, and alkyl, (hetero)aryl, and alkenyl groups, are well-tolerated under the reaction conditions. Furthermore, it allows a facile entry to the labile diarylacetaldehydes by TFA-mediated hydrolysis of β,β-disubstituted vinyl ethers.
An electric field-induced change in the selectivity of a metal oxide-catalyzed epoxide rearrangement
Gorin, Craig F.,Beh, Eugene S.,Kanan, Matthew W.
supporting information; experimental part, p. 186 - 189 (2012/03/07)
The rearrangement of cis-stilbene oxide catalyzed by Al2O 3 was studied in the presence of interfacial electric fields. Thin films of Al2O3 deposited on Si electrodes were used as the opposing walls of a reaction vessel. Application of a voltage across the electrodes engendered electrochemical double layer formation at the Al 2O3-solution interface. The aldehyde to ketone product ratio of the rearrangement was increased by up to a factor of 63 as the magnitude of the double layer charge density was increased. The results support a field-dipole effect on the selectivity of the catalytic reaction.
Bismuth(III) oxide perchlorate promoted rearrangement of epoxides to aldehydes and ketones
Anderson, Andrew M.,Blazek, Jesse M.,Garg, Parie,Payne, Brian J.,Mohan, Ram S.
, p. 1527 - 1530 (2007/10/03)
Aryl-substituted epoxides and aliphatic epoxides with a tertiary epoxide carbon undergo smooth rearrangement in the presence of 10-50 mol% bismuth(III) oxide perchlorate, BiOClO4·XH2O, to give carbonyl compounds. The rearrangement is regioselective with aryl substituted epoxides and a single carbonyl compound arising from cleavage of benzylic C-O bond is formed. BiOClO4·XH2O is relatively non-toxic, insensitive to air and inexpensive, making this catalyst an attractive alternative to more corrosive and toxic Lewis acids such as BF3·Et2O or INCl3 currently used to effect epoxide rearrangements. (C) 2000 Elsevier Science Ltd.
Diastereoselectivity in the reduction of sterically unbiased 2,2-diarylcyclopentanones
Halterman, Ronald L.,McEvoy, Marjorie A.
, p. 6690 - 6695 (2007/10/02)
Reduction of sterically unbiased 2-phenyl-2-(4-X-phenyl)cyclopentanones 1 (X = NO2, Br, Cl, OCH3, OH, NH2) with either sodium borohydride in methanol or lithium borohydride in tetrahydrofuran at 0°C produced diastereomeric
