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

Albert Cabré; Juanjo Cabezas-Giménez; Giuseppe Sciortino; Gregori Ujaque; Xavier Verdaguer; Agustí Lledós; Antoni Riera

doi:10.1002/adsc.201900372

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

Albert Cabré, Juanjo Cabezas-Giménez, Giuseppe Sciortino, Gregori Ujaque, Xavier Verdaguer, Agustí Lledós, Antoni Riera

Department of Chemistry

Research output: Contribution to journal › Article › Research

2 Citations (Scopus)

Abstract

© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 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.).

Original language	English
Pages (from-to)	3624-3631
Journal	Advanced Synthesis and Catalysis
Volume	361
DOIs	https://doi.org/10.1002/adsc.201900372
Publication status	Published - 1 Jan 2019

Keywords

Crabtree's catalyst
epoxides
iridium
isomerization
β-alkyl amines

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

abstract = "{\textcopyright} 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 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.).",

keywords = "Crabtree's catalyst, epoxides, iridium, isomerization, β-alkyl amines",

author = "Albert Cabr{\'e} and Juanjo Cabezas-Gim{\'e}nez and Giuseppe Sciortino and Gregori Ujaque and Xavier Verdaguer and Agust{\'i} Lled{\'o}s and Antoni Riera",

year = "2019",

month = jan,

day = "1",

doi = "10.1002/adsc.201900372",

language = "English",

volume = "361",

pages = "3624--3631",

journal = "Advanced Synthesis and Catalysis",

issn = "1615-4150",

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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.

In: Advanced Synthesis and Catalysis, Vol. 361, 01.01.2019, p. 3624-3631.

Research output: Contribution to journal › Article › Research

TY - JOUR

T1 - Mild Iridium-Catalysed Isomerization of Epoxides. Computational Insights and Application to the Synthesis of β-Alkyl Amines

AU - Cabré, Albert

AU - Cabezas-Giménez, Juanjo

AU - Sciortino, Giuseppe

AU - Ujaque, Gregori

AU - Verdaguer, Xavier

AU - Lledós, Agustí

AU - Riera, Antoni

PY - 2019/1/1

Y1 - 2019/1/1

N2 - © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 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.).

AB - © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 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.).

KW - Crabtree's catalyst

KW - epoxides

KW - iridium

KW - isomerization

KW - β-alkyl amines

U2 - 10.1002/adsc.201900372

DO - 10.1002/adsc.201900372

M3 - Article

VL - 361

SP - 3624

EP - 3631

JO - Advanced Synthesis and Catalysis

JF - Advanced Synthesis and Catalysis

SN - 1615-4150

ER -