Mild Iridium-Catalysed Isomerization of Epoxides. Computational Insights and Application to the Synthesis of β-Alkyl Amines
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.).
Cabré, Albert,Cabezas-Giménez, Juanjo,Sciortino, Giuseppe,Ujaque, Gregori,Verdaguer, Xavier,Lledós, Agustí,Riera, Antoni
supporting information
p. 3624 - 3631
(2019/07/10)
Isomerization of terminal epoxides by a [Pd-H] catalyst: A combined experimental and theoretical mechanistic study
An unusual palladium hydride complex has been shown to be a competent catalyst in the isomerization of a variety of terminal and internal epoxides. The reaction displayed broad scope and synthetic utility. Experimental and theoretical evidence are provided for an unprecedented hydride mechanism characterized by two distinct enantio-determining steps. These results hold promise for the development of an enantioselective variant of the reaction.
Solvent free synthetic procedure throughout reaction and separation: ylide reaction with alkyl aryl ketones in the absence of solvent followed by distillation to give 1-alkyl-1-aryloxiranes
After heating a mixture of trimethylsulphonium iodide, tBuOK and an alkyl aryl ketone at 60-70 °C for 1-5 h, vacuum distillation gave the corresponding 1-alkyl-1-aryloxirane. The procedure was accomplished without using any solvent throughout the reaction and the separation.
Toda, Fumio,Kanemoto, Kazuyuki
p. 185 - 188
(2007/10/03)
On acid-catalysed dehydration of 3-methyl-2-phenylbutan-2-ol
Dehydration of 3-methyl-2-phenylbutan-2-ol (I) using PTS as catalyst under mild conditions yields predominantly the anti-Saytzeff product, 3-methyl-2-phenyl-1-butene (II) which could be freed from its isomer, 2-methyl-3-phenyl-2-butene (III) by Ag+/
Gurudutt, K. N.,Shaw, A. K.
p. 422 - 423
(2007/10/02)
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