Aryl boronic acid-catalysed dehydrative substitution of benzylic alcohols for C-O bond formation

Susana Estopiñá-Durán; Liam  J. Donnelly; Euan  B. Mclean; Bryony  M. Hockin; Alexandra  M. Z. Slawin; James Taylor

doi:10.1002/chem.201806057

Aryl boronic acid-catalysed dehydrative substitution of benzylic alcohols for C-O bond formation

Susana Estopiñá-Durán, Liam J. Donnelly, Euan B. Mclean, Bryony M. Hockin, Alexandra M. Z. Slawin, James Taylor

Research output: Contribution to journal › Article › peer-review

Abstract

A combination of pentafluorophenylboronic acid and oxalic acid catalyses the dehydrative substitution of benzylic alcohols with a second alcohol to form new C-O bonds. This method has been applied to the intermolecular substitution of benzylic alcohols to form symmetrical ethers, intramolecular cyclisations of diols to form aryl-substituted tetrahydrofuran and tetrahydropyran derivatives, and intermolecular crossed-etherification reactions between two different alcohols. Mechanistic control experiments have identified a potential catalytic intermediate formed between the arylboronic acid and oxalic acid.

Original language	English
Pages (from-to)	3950-3956
Journal	Chemistry - A European Journal
Volume	25
Issue number	15
Early online date	11 Feb 2019
DOIs	https://doi.org/10.1002/chem.201806057
Publication status	Published - 12 Mar 2019

Keywords

Alcohols
Homogeneous catalysis
Boronic acids
Etherification
Substitution

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10.1002/chem.201806057

Taylor_2019_CEJ_Aryl_AAM
Copyright © 2019 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim. This work has been made available online in accordance with the publisher’s policies. This is the author created, accepted version manuscript following peer review and may differ slightly from the final published version. The final published version of this work is available at https://doi.org/10.1002/chem.201806057
Accepted author manuscript, 1.95 MB

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@article{90a4919994ed4224bca07a23d7d68b83,

title = "Aryl boronic acid-catalysed dehydrative substitution of benzylic alcohols for C-O bond formation",

abstract = "A combination of pentafluorophenylboronic acid and oxalic acid catalyses the dehydrative substitution of benzylic alcohols with a second alcohol to form new C-O bonds. This method has been applied to the intermolecular substitution of benzylic alcohols to form symmetrical ethers, intramolecular cyclisations of diols to form aryl-substituted tetrahydrofuran and tetrahydropyran derivatives, and intermolecular crossed-etherification reactions between two different alcohols. Mechanistic control experiments have identified a potential catalytic intermediate formed between the arylboronic acid and oxalic acid.",

keywords = "Alcohols, Homogeneous catalysis, Boronic acids, Etherification, Substitution",

author = "Susana Estopi{\~n}{\'a}-Dur{\'a}n and Donnelly, \{Liam J.\} and Mclean, \{Euan B.\} and Hockin, \{Bryony M.\} and Slawin, \{Alexandra M. Z.\} and James Taylor",

note = "We thank the University of St Andrews and the EPSRC for the award of a DTA studentship (S.E.-D.). We would also like to thank the EPSRC, University of St Andrews, and CRITICAT Centre for Doctoral Training for financial support [Ph.D. studentships to B.M.H, E.B.M and L.J.D; Grant code: EP/L016419/1]. J.E.T thanks the Leverhulme Trust for the award of an Early Career Fellowship (Grant code: ECF-2014-005).",

year = "2019",

month = mar,

day = "12",

doi = "10.1002/chem.201806057",

language = "English",

volume = "25",

pages = "3950--3956",

journal = "Chemistry - A European Journal",

issn = "0947-6539",

publisher = "John Wiley \& Sons, Ltd",

number = "15",

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TY - JOUR

T1 - Aryl boronic acid-catalysed dehydrative substitution of benzylic alcohols for C-O bond formation

AU - Estopiñá-Durán, Susana

AU - Donnelly, Liam J.

AU - Mclean, Euan B.

AU - Hockin, Bryony M.

AU - Slawin, Alexandra M. Z.

AU - Taylor, James

N1 - We thank the University of St Andrews and the EPSRC for the award of a DTA studentship (S.E.-D.). We would also like to thank the EPSRC, University of St Andrews, and CRITICAT Centre for Doctoral Training for financial support [Ph.D. studentships to B.M.H, E.B.M and L.J.D; Grant code: EP/L016419/1]. J.E.T thanks the Leverhulme Trust for the award of an Early Career Fellowship (Grant code: ECF-2014-005).

PY - 2019/3/12

Y1 - 2019/3/12

N2 - A combination of pentafluorophenylboronic acid and oxalic acid catalyses the dehydrative substitution of benzylic alcohols with a second alcohol to form new C-O bonds. This method has been applied to the intermolecular substitution of benzylic alcohols to form symmetrical ethers, intramolecular cyclisations of diols to form aryl-substituted tetrahydrofuran and tetrahydropyran derivatives, and intermolecular crossed-etherification reactions between two different alcohols. Mechanistic control experiments have identified a potential catalytic intermediate formed between the arylboronic acid and oxalic acid.

AB - A combination of pentafluorophenylboronic acid and oxalic acid catalyses the dehydrative substitution of benzylic alcohols with a second alcohol to form new C-O bonds. This method has been applied to the intermolecular substitution of benzylic alcohols to form symmetrical ethers, intramolecular cyclisations of diols to form aryl-substituted tetrahydrofuran and tetrahydropyran derivatives, and intermolecular crossed-etherification reactions between two different alcohols. Mechanistic control experiments have identified a potential catalytic intermediate formed between the arylboronic acid and oxalic acid.

KW - Alcohols

KW - Homogeneous catalysis

KW - Boronic acids

KW - Etherification

KW - Substitution

UR - https://www.scopus.com/pages/publications/85061377765

U2 - 10.1002/chem.201806057

DO - 10.1002/chem.201806057

M3 - Article

SN - 0947-6539

VL - 25

SP - 3950

EP - 3956

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 15

ER -

Aryl boronic acid-catalysed dehydrative substitution of benzylic alcohols for C-O bond formation

Abstract

Keywords

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Catalytic Activation: Catalytic Activation of Carboxylic Acids and Alcohols

CRITICAT CDT: Critical Resource Catalysis - CRITICAT

Data for Aryl boronic acid-catalysed dehydrative substitution of benzylic alcohols for C-O bond formation

Arylboronic acid-catalysed dehydrative substitution of alcohols

Evaluation of two- and three-coordinate copper(I) NHC complexes as photocatalysts

Cite this

Aryl boronic acid-catalysed dehydrative substitution of benzylic alcohols for C-O bond formation

Abstract

Keywords

Access to Document

Other files and links

Fingerprint

Projects

Catalytic Activation: Catalytic Activation of Carboxylic Acids and Alcohols

CRITICAT CDT: Critical Resource Catalysis - CRITICAT

Datasets

Data for Aryl boronic acid-catalysed dehydrative substitution of benzylic alcohols for C-O bond formation

Student theses

Arylboronic acid-catalysed dehydrative substitution of alcohols

Evaluation of two- and three-coordinate copper(I) NHC complexes as photocatalysts

Cite this