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

Simone Manzini, Albert Poater, David Nelson, Luigi Cavallo, Steven P. Nolan

Research output: Contribution to journalArticle

43 Citations (Scopus)

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.

LanguageEnglish
Pages180-188
Number of pages9
JournalChemical Science
Volume5
Issue number1
Early online date18 Oct 2013
DOIs
Publication statusPublished - 1 Jan 2014
Externally publishedYes

Fingerprint

Ruthenium
Isomerization
Catalysts
Design for testability
Deuterium
Ketones
Hydrides
Density functional theory
Experiments
Substrates
allyl alcohol
Temperature

Keywords

  • primary allylic alcohols
  • ketones
  • phenyl

Cite this

Manzini, Simone ; Poater, Albert ; Nelson, David ; Cavallo, Luigi ; Nolan, Steven P. / How phenyl makes a difference : mechanistic insights into the ruthenium(ii)-catalysed isomerisation of allylic alcohols. In: Chemical Science. 2014 ; Vol. 5, No. 1. pp. 180-188.
@article{a096545240864bc1b805cf7aad6dfe76,
title = "How phenyl makes a difference: mechanistic insights into the ruthenium(ii)-catalysed isomerisation of allylic alcohols",
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.",
keywords = "primary allylic alcohols, ketones, phenyl",
author = "Simone Manzini and Albert Poater and David Nelson and Luigi Cavallo and Nolan, {Steven P.}",
year = "2014",
month = "1",
day = "1",
doi = "10.1039/c3sc52612g",
language = "English",
volume = "5",
pages = "180--188",
journal = "Chemical Science",
issn = "2041-6520",
number = "1",

}

How phenyl makes a difference : mechanistic insights into the ruthenium(ii)-catalysed isomerisation of allylic alcohols. / Manzini, Simone; Poater, Albert; Nelson, David; Cavallo, Luigi; Nolan, Steven P.

In: Chemical Science, Vol. 5, No. 1, 01.01.2014, p. 180-188.

Research output: Contribution to journalArticle

TY - JOUR

T1 - How phenyl makes a difference

T2 - Chemical Science

AU - Manzini, Simone

AU - Poater, Albert

AU - Nelson, David

AU - Cavallo, Luigi

AU - Nolan, Steven P.

PY - 2014/1/1

Y1 - 2014/1/1

N2 - [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.

AB - [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.

KW - primary allylic alcohols

KW - ketones

KW - phenyl

UR - http://www.scopus.com/inward/record.url?scp=84888610152&partnerID=8YFLogxK

U2 - 10.1039/c3sc52612g

DO - 10.1039/c3sc52612g

M3 - Article

VL - 5

SP - 180

EP - 188

JO - Chemical Science

JF - Chemical Science

SN - 2041-6520

IS - 1

ER -