Organofluorine Chemistry: Techniques and Synthons

262 Pages·1997·5.38 MB·English

by  John Hutchinson

193
Topics in Current Chemistry
Editorial Board:
A.de Meijere · K.N.Houk · J.-M.Lehn · S.V.Ley
J.Thiem · B.M.Trost · F.Vögtle · H.Yamamoto
Springer
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Organofluorine Chemistry
Techniques and Synthons
Volume Editor: R.D.Chambers
With contributions by
D.J.Burton,F.G.Drakesmith,J.Hutchinson,
T.Kitazume,L.Lu,J.M.Percy,G.Sandford,
T.Yamazaki
123
This series presents critical reviews ofthe present position and future trends in
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Volume Editor
Prof.Richard D.Chambers,F.R.S.
Department ofChemistry
University ofDurham
South Road
Durham DH1 3LE,Great Britain
E-mail:R.Dr [email protected]
Editorial Board
Prof.Dr.Armin de Meijere Prof.K.N.Houk
Institut für Organische Chemie Department ofChemistry and Biochemistry
der Georg-August-Universität University ofCalifornia
Tammannstraße 2 405Higard Avenue
D-37077Göttingen,Germany Los Angeles,CA 90024-1589,USA
E-mail:[email protected] E-mail:[email protected]
Prof.Jean-Marie Lehn Prof.Steven V.Ley
Institut de Chimie University Chemical Laboratory
Université de Strasbourg Lensfield Road
1rue Blaise Pascal,B.P.Z 296/R8 Cambridge CB2 1EW,Great Britain
F-67008Strasbourg Cedex,France E-mail:[email protected]
E-mail:[email protected]
Prof.Dr.Joachim Thiem Prof.Barry M.Trost
Institut für Organische Chemie Department ofChemistry
Universität Hamburg Stanford University
Martin-Luther-King-Platz 6 Stanford,CA 94305-5080,USA
D-20146Hamburg,Germany E-mail:[email protected]
E-mail:[email protected]
Prof.Dr.Fritz Vögtle Prof.Hisashi Yamamoto
Institut für Organische Chemie School ofEngineering
und Biochemie der Universität Nagoya University
Gerhard-Domagk-Straße 1 Chikusa,Nagoya 464-01,Japan
D-53121Bonn,Germany E-mail:[email protected]
E-mail:[email protected]
Preface
Fluorine is unique in that it is possible to replace hydrogen by fluorine either
singly or multiply,in an organic molecule and,in so-doing create a potentially
infinite extension to organic chemistry that is entirely synthetic.The excitement
ofthe chemistry ofthese systems stems from the unique reactions that ensue and
the “special-effects”that introduction offluorine impart.Indeed,these effects are
now exploited in a remarkable array of applications across the whole of the
chemical,pharmaceutical,and plant-protection industries,although this is not
widely appreciated. In this book, we have gathered authors with immense
experience in various aspects oftheir field and each is a world-authority on the
important topics they have described. Some topics, like the use of elemental
fluorine, and enzymes in synthesis, are relatively new areas that are rapidly
growing.
We dedicate the book to a long standing friend,Professor George Olah,in the
year ofhis 70th birthday,in recognition ofhis massive achievements.
Durham,May 1997 Dick Chambers
Contents
Elemental Fluorine in Organic Chemistry
J.Hutchinson and G.Sandford . . . . . . . . . . . . . . . . . . . . . . . . 1
Fluorinated Organometallic Compounds
D.J.Burton and L.Lu . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
Enzymatically Controlled Reactions
ofOrganofluorine Compounds
T.Kitazume and T.Yamazaki . . . . . . . . . . . . . . . . . . . . . . . . . 91
Building Block Approaches to Aliphatic
Organofluorine Compounds
J.M.Percy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 131
Electrofluorination ofOrganic Compounds
F.G.Drakesmith . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 197
Author Index Volumes 151–193 . . . . . . . . . . . . . . . . . . . . . . . 243
Contents of Volume 192
Organofluorine Chemistry:Fluorinated Alkenes
and Reactive Intermediates
Volume Editor:R.D.Chambers
Nucleophilic Reactions ofFluorinated Alkenes
R.D.Chambers and J.F.S.Vaughan
Reactions ofElectrophiles with Polyfluorinated Olefins
V.A.Petrov and V.V.Bardin
Fluorinated Free Radicals
W.R.Dolbier,Jr.
Telomerisation Reactions ofFluorinated Alkenes
B.Améduri and B.Boutevin
Elemental Fluorine in Organic Chemistry
John Hutchinsona,b· Graham Sandfordb*
a B.N.F.L.Fluorochemicals Ltd.
b Department ofChemistry,University ofDurham,South Road,Durham,DH1 3LE,
Great Britain
E-mail:[email protected],E-mail:[email protected]
There is a gradual realisation that elemental fluorine,for a long time considered too reactive
and uncontrollable,can be used in viable syntheses on both the laboratory and industrial scale.
This review focuses on recent uses of fluorine for the preparation of perfluorinated and
selectively fluorinated molecules as well as for the promotion ofother organic transformations.
Keywords: Elemental fluorine,direct fluorination.
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2 Perfluorination . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.1 Mechanistic Considerations . . . . . . . . . . . . . . . . . . . . . 3
2.2 Hydrocarbons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
2.3 Haloalkanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
2.4 Ethers and Polyethers . . . . . . . . . . . . . . . . . . . . . . . . . 11
2.5 Ketones,Esters and Related Compounds . . . . . . . . . . . . . . 13
2.6 Substrates Containing Nitrogen,Sulfur or Phosphorous . . . . . 15
2.7 Carbon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
3 Selective Direct Fluorination . . . . . . . . . . . . . . . . . . . . 17
3.1 Preparation ofCarbon-Fluorine Bonds . . . . . . . . . . . . . . . 17
3.1.1 Replacement ofHydrogen by Fluorine . . . . . . . . . . . . . . . 17
3.1.1.1 Alkanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
3.1.1.2 Carbonyl Compounds . . . . . . . . . . . . . . . . . . . . . . . . 18
3.1.1.3 Benzenoid Compounds . . . . . . . . . . . . . . . . . . . . . . . . 21
3.1.1.4 Heterocyclic Aromatic Compounds . . . . . . . . . . . . . . . . . 23
3.1.2 Fluorodesulfurization Reactions . . . . . . . . . . . . . . . . . . . 26
3.1.3 Fluorodemetallisation . . . . . . . . . . . . . . . . . . . . . . . . 27
3.1.4 Addition ofFluorine to Carbon-Carbon Double Bonds . . . . . . 28
3.2 Preparation ofOxygen-Fluorine Bonds . . . . . . . . . . . . . . . 31
3.2.1 Perfluoroalkyl,Acyl and Perfluoroacyl Hypofluorites . . . . . . . 31
3.2.2 Alkyl Hypofluorites . . . . . . . . . . . . . . . . . . . . . . . . . . 32
3.3 Preparation ofNitrogen-Fluorine Bonds . . . . . . . . . . . . . . 32
* Corresponding author.
Topics in Current Chemistry,Vol.193
© Springer Verlag Berlin Heidelberg 1997
2 J.Hutchinson · G.Sandford
4 Fluorine as a Reagent for the Synthesis of
Non-Fluorinated Compounds . . . . . . . . . . . . . . . . . . . . 33
4.1 Organic Transformations Promoted by Fluorine . . . . . . . . . . 33
5 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
1
Introduction
With a few exceptions,carbon-fluorine bonds are not found in nature and so the
enormous range of molecules that have been prepared which contain fluorine
are essentially man-made [1].Ofparamount importance,therefore,for the deve-
lopment of organofluorine chemistry,is the invention of simple,effective and
highly efficient methods for the introduction offluorine into organic substrates
and many approaches utilising various reagents have been studied and adopted,
as detailed in several recent reviews [2–7].
The effect of introducing one or several fluorine atoms into an organic sub-
strate can have a profound effect on the physical,chemical and biological pro-
perties ofthe molecule and this is exemplified by the growing number ofpharma-
ceuticals and plant protection agents that have fluorine atoms incorporated in
their structure [8].More extensively fluorinated compounds,as well as having a
distinct and rich chemistry [1,9,10],have also found many commercial appli-
cations [8].
In this chapter we will focus on the rapidly expanding area concerning the
use ofelemental fluorine for the preparation oforganic compounds containing
bonds between fluorine and carbon,oxygen,nitrogen,sulfur or phosphorous.
The preparation of perfluorinated compounds by direct fluorination method-
ology (Section 2) was last reviewed by Lagow [11] in 1979 whilst the preparation
of selectively fluorinated compounds,that is substrates containing one or two
fluorine atoms, by direct fluorination (Sect. 3), was last comprehensively re-
viewed by Purrington [12] in 1986, although other articles have since been
published [10,13–19] which are concerned with specific aspects ofboth ofthese
areas.The present chapter aims to present developments in the use of direct
fluorination since these last two major reviews as well as to provide an overview
of the more significant mechanistic aspects concerning such processes. A
discussion ofthe processes in which fluorine may be used for the promotion of
organic transformations which do not result in the introduction offluorine into
the substrate is also included (Sect.4).
Elemental fluorine was first prepared in small quantities by Henri Moissan
[20,21] in Paris in 1886 by the electrolysis ofa solution ofanhydrous hydrogen
fluoride which contained a small amount of potassium fluoride.This method
remains in use today, as the generation of fluorine is carried out on the in-
dustrial scale,largely for use in the nuclear electricity generating industry,by
electrolysis ofKF·2HF.This electrolyte melts at about 100°C,allowing the cells
to be operated at reasonable temperatures [22].Several chemical methods for
the generation offluorine have recently been reported [23–26].