Lewis acid-promoted hydrofluorination of alkynyl sulfides to generate α-fluorovinyl thioethers

Davide Bello; David O'Hagan

doi:10.3762/bjoc.11.205

Lewis acid-promoted hydrofluorination of alkynyl sulfides to generate α-fluorovinyl thioethers

Davide Bello, David O'Hagan^*

^*Corresponding author for this work

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

Abstract

A new method for the preparation of alpha-fluorovinyl thioethers is reported which involves the hydrofluorination of alkynyl sulfides with 3HF center dot Et₃N, a process that requires Lewis acid activation using BF₃ center dot Et₂O and TiF₄. The method gives access to a range of α-fluorovinyl thioethers, some in high stereoselectivity with the Z-isomer predominating over the E-isomer. The α-fluorovinyl thioether motif has prospects as a steric and electronic mimetic of thioester enols and enolates, important intermediates in enzymatic C-C bond forming reactions. The method opens access to appropriate analogues for investigations in this direction.

Original language	English
Pages (from-to)	1902-1909
Number of pages	8
Journal	Beilstein Journal of Organic Chemistry
Volume	11
DOIs	https://doi.org/10.3762/bjoc.11.205
Publication status	Published - 14 Oct 2015

Keywords

Alkynyl sulfides
Alpha-fluorovinyl thioethers
Hydrofluorination
Lewis acids
Organofluorine
Efficient catalyst
Vinyl sulfides
Thiols
Substrate
Mimetics
Flouride

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10.3762/bjoc.11.205

OHagan_2015_BJOC_Lewis_CC
© 2015 Bello and O'Hagan; licensee Beilstein-Institut. This is an Open Access article under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/2.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
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title = "Lewis acid-promoted hydrofluorination of alkynyl sulfides to generate α-fluorovinyl thioethers",

abstract = "A new method for the preparation of alpha-fluorovinyl thioethers is reported which involves the hydrofluorination of alkynyl sulfides with 3HF center dot Et3N, a process that requires Lewis acid activation using BF3 center dot Et2O and TiF4. The method gives access to a range of α-fluorovinyl thioethers, some in high stereoselectivity with the Z-isomer predominating over the E-isomer. The α-fluorovinyl thioether motif has prospects as a steric and electronic mimetic of thioester enols and enolates, important intermediates in enzymatic C-C bond forming reactions. The method opens access to appropriate analogues for investigations in this direction.",

keywords = "Alkynyl sulfides, Alpha-fluorovinyl thioethers, Hydrofluorination, Lewis acids, Organofluorine, Efficient catalyst, Vinyl sulfides, Thiols, Substrate, Mimetics, Flouride",

author = "Davide Bello and David O'Hagan",

note = "The authors thank EPSRC for supporting this work and DO{\textquoteright}H is grateful for a Royal Society Wolfson Research Merit Award. ",

year = "2015",

month = oct,

day = "14",

doi = "10.3762/bjoc.11.205",

language = "English",

volume = "11",

pages = "1902--1909",

journal = "Beilstein Journal of Organic Chemistry",

issn = "1860-5397",

publisher = "Beilstein-Institut Zur Forderung der Chemischen Wissenschaften",

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TY - JOUR

T1 - Lewis acid-promoted hydrofluorination of alkynyl sulfides to generate α-fluorovinyl thioethers

AU - Bello, Davide

AU - O'Hagan, David

N1 - The authors thank EPSRC for supporting this work and DO’H is grateful for a Royal Society Wolfson Research Merit Award.

PY - 2015/10/14

Y1 - 2015/10/14

N2 - A new method for the preparation of alpha-fluorovinyl thioethers is reported which involves the hydrofluorination of alkynyl sulfides with 3HF center dot Et3N, a process that requires Lewis acid activation using BF3 center dot Et2O and TiF4. The method gives access to a range of α-fluorovinyl thioethers, some in high stereoselectivity with the Z-isomer predominating over the E-isomer. The α-fluorovinyl thioether motif has prospects as a steric and electronic mimetic of thioester enols and enolates, important intermediates in enzymatic C-C bond forming reactions. The method opens access to appropriate analogues for investigations in this direction.

AB - A new method for the preparation of alpha-fluorovinyl thioethers is reported which involves the hydrofluorination of alkynyl sulfides with 3HF center dot Et3N, a process that requires Lewis acid activation using BF3 center dot Et2O and TiF4. The method gives access to a range of α-fluorovinyl thioethers, some in high stereoselectivity with the Z-isomer predominating over the E-isomer. The α-fluorovinyl thioether motif has prospects as a steric and electronic mimetic of thioester enols and enolates, important intermediates in enzymatic C-C bond forming reactions. The method opens access to appropriate analogues for investigations in this direction.

KW - Alkynyl sulfides

KW - Alpha-fluorovinyl thioethers

KW - Hydrofluorination

KW - Lewis acids

KW - Organofluorine

KW - Efficient catalyst

KW - Vinyl sulfides

KW - Thiols

KW - Substrate

KW - Mimetics

KW - Flouride

UR - http://www.beilstein-journals.org/bjoc/single/articleFullText.htm?publicId=1860-5397-11-205#supporting-info

UR - https://www.scopus.com/pages/publications/84962200811

U2 - 10.3762/bjoc.11.205

DO - 10.3762/bjoc.11.205

M3 - Article

SN - 1860-5397

VL - 11

SP - 1902

EP - 1909

JO - Beilstein Journal of Organic Chemistry

JF - Beilstein Journal of Organic Chemistry

ER -

Lewis acid-promoted hydrofluorination of alkynyl sulfides to generate α-fluorovinyl thioethers

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Keywords

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