Hydrofluorination of alkynes catalysed by gold bifluorides

F. Nahra; S.R. Patrick; D. Bello; M. Brill; A. Obled; D.B. Cordes; A.M.Z. Slawin; D. O'Hagan; S.P. Nolan

doi:10.1002/cctc.201402891

Hydrofluorination of alkynes catalysed by gold bifluorides

F. Nahra, S.R. Patrick, D. Bello, M. Brill, A. Obled, D.B. Cordes, A.M.Z. Slawin, D. O'Hagan, S.P. Nolan

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

Abstract

We report the synthesis of nine new N-heterocyclic carbene gold bifluoride complexes starting from the corresponding N-heterocyclic carbene gold hydroxides. A new methodology to access N,N′-bis(2,6-diisopropylphenyl)imidazol-2-ylidene gold(I) fluoride starting from N,N′-bis(2,6-diisopropylphenyl)imidazol-2-ylidene gold(I) hydroxide and readily available potassium bifluoride is also reported. These gold bifluorides were shown to be efficient catalysts in the hydrofluorination of symmetrical and unsymmetrical alkynes, thus affording fluorinated stilbene analogues and fluorovinyl thioethers in good to excellent yields with high stereo- and regioselectivity. The method is exploited further to access a fluorinated combretastatin analogue selectively in two steps starting from commercially available reagents.

Original language	English
Pages (from-to)	240-244
Number of pages	5
Journal	ChemCatChem
Volume	7
Issue number	2
Early online date	26 Nov 2014
DOIs	https://doi.org/10.1002/cctc.201402891
Publication status	Published - Jan 2015

Keywords

Alkynes
Bifluorides
Gold
Hydrofluorination
Carbenes

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10.1002/cctc.201402891

Nahra_et_al-2015-ChemCatChem
Copyright 2015 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
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title = "Hydrofluorination of alkynes catalysed by gold bifluorides",

abstract = "We report the synthesis of nine new N-heterocyclic carbene gold bifluoride complexes starting from the corresponding N-heterocyclic carbene gold hydroxides. A new methodology to access N,N′-bis(2,6-diisopropylphenyl)imidazol-2-ylidene gold(I) fluoride starting from N,N′-bis(2,6-diisopropylphenyl)imidazol-2-ylidene gold(I) hydroxide and readily available potassium bifluoride is also reported. These gold bifluorides were shown to be efficient catalysts in the hydrofluorination of symmetrical and unsymmetrical alkynes, thus affording fluorinated stilbene analogues and fluorovinyl thioethers in good to excellent yields with high stereo- and regioselectivity. The method is exploited further to access a fluorinated combretastatin analogue selectively in two steps starting from commercially available reagents.",

keywords = "Alkynes, Bifluorides, Gold, Hydrofluorination, Carbenes",

author = "F. Nahra and S.R. Patrick and D. Bello and M. Brill and A. Obled and D.B. Cordes and A.M.Z. Slawin and D. O'Hagan and S.P. Nolan",

note = "The ERC (Advanced Investigator Award FUNCAT and PoC award GOLDCAT), the EPSRC and Syngenta are gratefully acknowledged for support of this work. Umicore AG is acknowledged for their generous gift of auric acid. S.P.N. is a Royal Society Wolfson Research Merit Award holder.",

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doi = "10.1002/cctc.201402891",

language = "English",

volume = "7",

pages = "240--244",

journal = "ChemCatChem",

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T1 - Hydrofluorination of alkynes catalysed by gold bifluorides

AU - Nahra, F.

AU - Patrick, S.R.

AU - Bello, D.

AU - Brill, M.

AU - Obled, A.

AU - Cordes, D.B.

AU - Slawin, A.M.Z.

AU - O'Hagan, D.

AU - Nolan, S.P.

N1 - The ERC (Advanced Investigator Award FUNCAT and PoC award GOLDCAT), the EPSRC and Syngenta are gratefully acknowledged for support of this work. Umicore AG is acknowledged for their generous gift of auric acid. S.P.N. is a Royal Society Wolfson Research Merit Award holder.

PY - 2015/1

Y1 - 2015/1

N2 - We report the synthesis of nine new N-heterocyclic carbene gold bifluoride complexes starting from the corresponding N-heterocyclic carbene gold hydroxides. A new methodology to access N,N′-bis(2,6-diisopropylphenyl)imidazol-2-ylidene gold(I) fluoride starting from N,N′-bis(2,6-diisopropylphenyl)imidazol-2-ylidene gold(I) hydroxide and readily available potassium bifluoride is also reported. These gold bifluorides were shown to be efficient catalysts in the hydrofluorination of symmetrical and unsymmetrical alkynes, thus affording fluorinated stilbene analogues and fluorovinyl thioethers in good to excellent yields with high stereo- and regioselectivity. The method is exploited further to access a fluorinated combretastatin analogue selectively in two steps starting from commercially available reagents.

AB - We report the synthesis of nine new N-heterocyclic carbene gold bifluoride complexes starting from the corresponding N-heterocyclic carbene gold hydroxides. A new methodology to access N,N′-bis(2,6-diisopropylphenyl)imidazol-2-ylidene gold(I) fluoride starting from N,N′-bis(2,6-diisopropylphenyl)imidazol-2-ylidene gold(I) hydroxide and readily available potassium bifluoride is also reported. These gold bifluorides were shown to be efficient catalysts in the hydrofluorination of symmetrical and unsymmetrical alkynes, thus affording fluorinated stilbene analogues and fluorovinyl thioethers in good to excellent yields with high stereo- and regioselectivity. The method is exploited further to access a fluorinated combretastatin analogue selectively in two steps starting from commercially available reagents.

KW - Alkynes

KW - Bifluorides

KW - Gold

KW - Hydrofluorination

KW - Carbenes

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U2 - 10.1002/cctc.201402891

DO - 10.1002/cctc.201402891

M3 - Article

AN - SCOPUS:84920822090

SN - 1867-3880

VL - 7

SP - 240

EP - 244

JO - ChemCatChem

JF - ChemCatChem

IS - 2

ER -

Hydrofluorination of alkynes catalysed by gold bifluorides

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GOLDCAT: EU FP7 ERC PoC GOLDCAT

Structuring the Future: Structuring the Future - Underpinning world-leading science in EaStCHEM through cutting edge characterisation

EPSRC - EP/J011053/1- LATE TRANSITION: Late Transition Metal Hydroxide in Homogeneous Catalysis