Mild Iridium-Catalysed Isomerization of Epoxides. Computational Insights and Application to the Synthesis of β-Alkyl Amines

In the presence of 3-5 mol% Crabtree's catalyst or the corresponding tetrakis[3,5-bis(trifluoromethyl)phenyl]borate salt (Cy3P)Ir+(pyridine)(1,5-cyclooctadiene)·X- {X = PF6, [3,5-(F3C)2C6H3]4B}, aryl 1,1-disubstituted epoxides such as α-methylstyrene oxide underwent chemoselective isomerization...

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Detalles Bibliográficos
Autores: Cabré Montesinos, Albert, Cabezas Giménez, Juan José, Sciortino, Giuseppe, Ujaque, Gregori, Verdaguer i Espaulella, Xavier, Lledós, Agustí (Lledós i Falcó), Riera i Escalé, Antoni
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2019
País:España
Institución:Universidad de Barcelona
Repositorio:Dipòsit Digital de la UB
OAI Identifier:oai:diposit.ub.edu:2445/143377
Acceso en línea:https://hdl.handle.net/2445/143377
Access Level:acceso abierto
Palabra clave:Iridi
Isomerització
Iridium
Isomerization
Descripción
Sumario:In the presence of 3-5 mol% Crabtree's catalyst or the corresponding tetrakis[3,5-bis(trifluoromethyl)phenyl]borate salt (Cy3P)Ir+(pyridine)(1,5-cyclooctadiene)·X- {X = PF6, [3,5-(F3C)2C6H3]4B}, aryl 1,1-disubstituted epoxides such as α-methylstyrene oxide underwent chemoselective isomerization to aldehydes; treatment with benzhydrylamine and pyrrolidine and redn. with NaBH4 yielded 2,2-disubstituted amines such as PhCHMeCH2NHR [R = Ph2CH, 4-MeOC6H4, PhCH2, (R)-PhCHMe] in one pot. DFT calcns. were performed to rationalize the obsd. selectivity.