Catalytic regioselective isomerization of 2,2-disubstituted oxetanes to homoallylic alcohols
Cabré, Albert (Universitat de Barcelona. Departament de Química Inorgànica i Orgànica)
Rafael, Sergi (Universitat de Barcelona. Departament de Química Inorgànica i Orgànica)
Sciortino, Giuseppe (Universitat Autònoma de Barcelona. Departament de Química)
Ujaque Pérez, Gregori (Universitat Autònoma de Barcelona. Departament de Química)
Verdaguer, Xavier (Universitat de Barcelona. Departament de Química Inorgànica i Orgànica)
Lledós, Agustí (Universitat Autònoma de Barcelona. Departament de Química)
Riera, Antoni (Universitat de Barcelona. Departament de Química Inorgànica i Orgànica)

Date:	2020
Description:	8 pàg.
Abstract:	The selective isomerization of strained heterocyclic compounds is an important tool in organic synthesis. An unprecedented regioselective isomerization of 2,2-disubstituted oxetanes into homoallylic alcohols is described. The use of tris(pentafluorophenyl)borane (B(C6F5)3), a commercially available Lewis acid was key to obtaining good yields and selectivities since other Lewis acids afforded mixtures of isomers and substantial polymerization. The reaction took place under exceptionally mild reaction conditions and very low catalyst loading (0. 5 mol %). DFT calculations disclose the mechanistic features of the isomerization and account for the high selectivity displayed by the B(C6F5)3 catalyst. The synthetic applicability of the new reaction is demonstrated by the preparation of γ-chiral alcohols using iridium-catalyzed asymmetric hydrogenation.
Grants:	Ministerio de Economía y Competitividad CTQ2017-87840-P Ministerio de Economía y Competitividad CTQ2017-87889-P
Rights:	Tots els drets reservats.
Language:	Anglès
Document:	Article ; recerca ; Versió acceptada per publicar
Subject:	Allylic compounds ; Asymmetric catalysis ; Boron ; Hydrogenation ; Isomerization
Published in:	Angewandte Chemie (International ed. Internet), Vol. 59, issue 19 (May 2020) , p. 7521-7527, ISSN 1521-3773

DOI: 10.1002/anie.201915772
PMID: 31981390

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