Mild Iridium‐Catalysed Isomerization of Epoxides. Computational Insights and Application to the Synthesis of β‐Alkyl Amines. Issue 15 (1st July 2019)

• Record Type: Journal Article
• Authors: Cabré, Albert; Cabezas‐Giménez, Juanjo; Sciortino, Giuseppe; Ujaque, Gregori; Verdaguer, Xavier; Lledós, Agustí; Riera, Antoni
• Is Part Of: Advanced synthesis & catalysis. Volume 361:Issue 15(2019)
• Page Start: 3624
• Page End: 3631
• Publication Date: 2019-07-01
• Subjects: iridium -- epoxides -- isomerization -- Crabtree's catalyst -- β-alkyl amines; Catalysis -- Periodicals; Organic compounds -- Synthesis -- Periodicals; Chemistry -- Periodicals; Chemistry, Technical -- Periodicals; Chemistry -- Periodicals; Catalysis -- Periodicals; Technology, Pharmaceutical -- Periodicals; 547.2
• DOI: 10.1002/adsc.201900372
• Languages: English
• ISSNs: 1615-4150

Abstract

Abstract: 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. Abstract :