Organofluorine Chemistry: Fluorinated Alkenes and Reactive Intermediates

255 Pages·1997·12.22 MB·English

by  R. D. Chambers

192
Topics in Current Chemistry
EditorialBoard:
A.deMeijere· K.N.Honk·J.-M.Lehn·S.V.Ley
J.Thiem·B.M.Trost·F.Vogtle·H.Yamamoto
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Organofluorine Chemistry
Fluorinated Alkenes
and Reactive Intermediates
Volume Editor: R.D. Chambers
With contributions by
B.Ameduri)V.V.Bardin)B.Boutevin)
R.D. Chambers)W.R.Dolbier)Jr.)
u.
A. Petrov)J.F.S.Vaughan
Springer
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Volume Editor
Prof.Richard D.Chambers,F.R.S.
DepartmentofChemistry
UniversityofDurham
SouthRoad
DH13LEDurham,GreatBritain
E-mail:[email protected]
Editorial Board
Prof.Dr.ArmindeMeijere Prof.K.N.Houk
InstitutfurOrganischeChemie DepartmentofChemistryandBiochemistry
derGeorg-August-UniversiHit UniversityofCalifornia
TammannstraBe2 405HigardAvenue
D-37077Gottingen,Germany LosAngeles,CA90024-1589,USA
E-mail:[email protected] E-mail:[email protected]
Prof.Jean-MarieLehn Prof.StevenV.Ley
InstitutdeChimie UniversityChemicalLaboratory
UniversitedeStrasbourg LensfieldRoad
1rueBlaisePascal,B.P.Z296/R8 CB2 lEWCambridge,GreatBritain
F-67008StrasbourgCedex,France E-mail:[email protected]
E-mail:[email protected]
Prof.Dr.JoachimThiem Prof.BarryM.Trost
InstitutfurOrganischeChemie DepartmentofChemistry
UniversiHitHamburg StanfordUniversity
Martin-Luther-King-Platz6 Stanford,CA94305-5080,USA
D-20146Hamburg,Germany E-mail:[email protected]
E-mail:[email protected]
Prof.Dr.FritzVogtle Prof.HisashiYamamoto
InstitutfurOrganischeChemie SchoolofEngineering
undBiochemiederUniversitat NagoyaUniversity
Gerhard-Domagk-StraBe1 464-01 Chikusa,Nagoya,Japan
D-53121 Bonn,Germany E-mail:[email protected]
E-mail:[email protected]
ecaferP
Fluorine is unique, in that it is possible to replace hydrogen in an organic mole-
cule by fluorine either singly or multiply and, in so-doing, create a potentially
infinite extension to organic chemistry that is entirely synthetic. The excitement
of the chemistry of these systems stems from the unique reactions that ensue and
the 'special-effects' that introduction of fluorine 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 of their 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.
eW dedicate the book to a long standing friend, Professor George Olah, in the
year of his 70th birthday, in recognition of his massive achievements.
Durham, May 1997 Dick Chambers
Contents
NucleophilicReactionsofFluorinatedAlkenes
R.D.ChambersandJ.F.S.Vaughan .
ReactionsofElectrophileswithPolyfluorinatedOlefins
U.A.PetrovandV.V. Bardin . . . . . . . . . . . . . . . . 39
FluorinatedFreeRadicals
W.R.Dolbier,Jr. . . . . . . 97
TelomerisationReactionsofFluorinatedAlkenes
B.AmeduriandB.Boutevin .. 165
AuthorIndexVolumes151-192 235
Contents ofVolume 193
OrganofluorineChemistry:Techniques
and Synthous
VolumeEditor:R.D.Chambers
ElementalFluorineinOrganicChemistry
J.HutchinsonandG.Sandford
FluorinatedOrganometallicCompounds
D.V.Burtonand1.Lu
EnzymaticallyControlledReactions
ofOrganofluorineCompounds
T.KitazumeandT.Yamazaki
BuildingBlockApproachestoAliphatic
OrganofluorineCompounds
J.M.Percy
ElectrofluorinationofOrganicCompounds
F.G.Drakesmith
Nucleophilic Reactions of Fluorinated seneklA
R. D. Chambers and . F. S. Vaughan
Department of Chemistry, University of Durham, South Road, Durham, DH1 3LE, U.K.
E-mail: r.d.chambers @ durham, ac. uk
Fluorinated -alkenes and -cycloalkenes have a special relationship with their hydrocarbon
analogues, usually exhibiting a chemistry that is complementary. For example, the fluorinated
systems are frequently susceptible to nucleophilic attack, in some cases dramatically so, and
therefore reactions of nucleophiles with fluorinated alkenes often reveal unique new chem-
istry. This chapter covers electrochemical reduction, principles governing orientation and
reactivity of fluorinated alkenes towards nucleophiles, fluoride ion as a nucleophile and the
'mirror-image' relationship of this chemistry with that of proton-induced reactions, reactions
with nitrogen-, oxygen-, carbon- centred nucleophiles etc., and, finally, chemistry of some
oligomers of fluorinated -alkenes and -cycloalkenes.
:sdrowyeK Fluorinated alkenes; nucleophilic attack; fluoride ion; oligomerisation; rearrange-
ments; displacement; carbanions.
1 Introduction ................................ 2
2 Substituent Effects of Fluorine and Perfluoroalkyl Groups ...... 3
3 Electrochemistry and Related Electron-Transfer Processes ..... 4
4 Reactivity and Regiochemistry of Nucleophilic Attack ........ 9
5 Reactions Involving Fluoride Ion .................... 11
5.1 Additions ................................. 13
5.2 Nucleophilic Analogues of Friedel Crafts Reactions .......... 13
5.3 Oligomerisation .............................. 14
5.4 Rearrangements .............................. 16
6 Attack by O, S and N Centred Nucleophiles ............... 18
7 Carbon Nucleophiles ........................... 24
8 Hydride Reductions ............................ 26
9 Reactions of Oligomers .......................... 27
References
. . . . . . . . . . . . . . . . . . . . (cid:12)9 ~ . . . . * . . . . . (cid:12)9 ~ (cid:12)9 (cid:12)9 35
scipoT in Current Chemistry, .loV 291
(cid:14)9 Springer galreV Berlin Heidelberg 7991