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How phenyl makes a difference : Mechanistic insights into the ruthenium(ii)-catalysed isomerisation of allylic alcohols

[RuCl(η5-3-phenylindenyl)(PPh3)2] (1) has been shown to be a highly active catalyst for the isomerisation of allylic alcohols to the corresponding ketones. A variety of substrates undergo the transformation, typically with 0.25-0.5 mol% of catalyst at room temperature, outperforming commonly-used complexes such as [RuCl(Cp)(PPh3) 2] and [RuCl(η5-indenyl)(PPh3) 2]. Mechanistic experiments and density functional theory have been employed to investigate the mechanism and understand the effect of catalyst structure on reactivity. These investigations suggest a oxo-π-allyl mechanism is in operation, avoiding intermediate ruthenium hydride complexes and leading to a characteristic 1,3-deuterium shift. Important mechanistic insights from DFT and experiments also allowed for the design of a protocol that expands the scope of the transformation to include primary allylic alcohols

We thank the ERC (Advanced Investigator Award ` FUNCAT’ to SPN) and the EPSRC for funding. Umicore is thanked for gi. s of materials. SPN is a Royal Society Wolfson Merit Award holder. Melanja Smith and Dr Tomas Lebl are thanked for assistance with NMR spectroscopy facilities. Dr Cesar A. Urbina-Blanco is acknowledged for useful discussions. LC thanks the HPC team of Enea for using the ENEA-GRID and the HPC facilities CRESCO in Portici (Italy) for access to remarkable computational resources. AP thanks the Spanish MICINN for a Ramon y Cajal contract (RYC-2009-05226) and European Commission for a Career Integration Grant (CIG09-GA-2011-293900)

© Chemical Science, 2014, vol. 5, p. 180-188

Royal Society of Chemistry (RSC)

Author: Manzini, Simone
Poater Teixidor, Albert
Nelson, David J.
Cavallo, Luigi
Nolan, Steven P.
Date: 2014
Abstract: [RuCl(η5-3-phenylindenyl)(PPh3)2] (1) has been shown to be a highly active catalyst for the isomerisation of allylic alcohols to the corresponding ketones. A variety of substrates undergo the transformation, typically with 0.25-0.5 mol% of catalyst at room temperature, outperforming commonly-used complexes such as [RuCl(Cp)(PPh3) 2] and [RuCl(η5-indenyl)(PPh3) 2]. Mechanistic experiments and density functional theory have been employed to investigate the mechanism and understand the effect of catalyst structure on reactivity. These investigations suggest a oxo-π-allyl mechanism is in operation, avoiding intermediate ruthenium hydride complexes and leading to a characteristic 1,3-deuterium shift. Important mechanistic insights from DFT and experiments also allowed for the design of a protocol that expands the scope of the transformation to include primary allylic alcohols
We thank the ERC (Advanced Investigator Award ` FUNCAT’ to SPN) and the EPSRC for funding. Umicore is thanked for gi. s of materials. SPN is a Royal Society Wolfson Merit Award holder. Melanja Smith and Dr Tomas Lebl are thanked for assistance with NMR spectroscopy facilities. Dr Cesar A. Urbina-Blanco is acknowledged for useful discussions. LC thanks the HPC team of Enea for using the ENEA-GRID and the HPC facilities CRESCO in Portici (Italy) for access to remarkable computational resources. AP thanks the Spanish MICINN for a Ramon y Cajal contract (RYC-2009-05226) and European Commission for a Career Integration Grant (CIG09-GA-2011-293900)
Format: application/pdf
ISSN: 2041-6520 (versió paper)
2041-6539 (versió electrònica)
Document access: http://hdl.handle.net/10256/10350
Language: eng
Publisher: Royal Society of Chemistry (RSC)
Collection: MICINN/PN 2012-2015/RYC-2009-05226
Reproducció digital del document publicat a: http://dx.doi.org/10.1039/c3sc52612g
Articles publicats (D-Q)
info:eu-repo/grantAgreement/EC/FP7/293900
Is part of: © Chemical Science, 2014, vol. 5, p. 180-188
Rights: Reconeixement 3.0 Espanya
Rights URI: http://creativecommons.org/licenses/by/3.0/es/deed.ca
Subject: Isomerització
Isomerization
Ruteni
Ruthenium
Mecanismes de reacció (Química)
Reaction mechanisms (Chemistry)
Funcional de densitat, Teoria del
Density functionals
Catalitzadors
Catalysts
Title: How phenyl makes a difference : Mechanistic insights into the ruthenium(ii)-catalysed isomerisation of allylic alcohols
Type: info:eu-repo/semantics/article
Repository: DUGiDocs

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