Best Synthetic Methods: Acetylenes, Allenes and Cumulenes (Best Synthetic Methods)

503 Pages·2004·2.75 MB·English

by  Lambert Brandsma

Synthesis of Acetylenes, Allenes and
Cumulenes: Methods and Techniques
BEST SYNTHETIC METHODS
Brandsma:SynthesisofAcetylenes,AllenesandCumulenes:MethodsandTechniques,2004
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Synthesis of Acetylenes,
Allenes and Cumulenes:
Methods and Techniques
Lambert Brandsma
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Preface
By combining and updating my previous laboratory manuals (1971, 1981 and
1988),thisbookdocumentsthemostimportantsyntheticmethodsinthefields
of acetylenes, allenes and cumulenes, as well as isolation techniques for
compounds with low stability or high volatility, illustrating experimental
proceduresonapreparativescalethatwereeithercarriedoutbytheauthoror
underhisclosesupervision.Mostprocedureshavebeenupdated,withsomeof
the original procedures that seemed unsafe or time-consuming being replaced
by easier alternatives.
Some useful practical tips are provided in the first chapter and in a number
of procedures explanation is given about the reaction conditions applied. In
mostcases,however,theseimplicitlyreflecttheknowledgeaboutreactivityand
reaction mechanisms in the field, acquired from the literature and during
extensive bench experience.
During the last 10 to 15 years the safety rules for experimentation have
become much more severe. A number of reagents and solvents are no longer
commercially available or have become extremely expensive. In practical
courses syntheses are now carried out on a much smaller scale for reasons of
safety and economy. The changed situation is taken into account in this new
work by the inclusion of procedures and results for smaller scale reactions. In
some procedures DMSO is used as a solvent instead of HMPT, which is
considered to be a carcinogen. Some procedures present the use of organic
solvents(e.g.DMSO–THF)asanalternativetoperformingreactionsinliquid
ammonia, which often has to be freed from water by a time-consuming,
evaporation-condensation operation. A number of procedures from more
recent research in the author’s group as well as several selected unchecked
methods from the literature are included, mostly in tabular form.
IamverygratefulforthepleasantandfruitfulcooperationofMrHermann
D.VerkruijssethatIhaveenjoyedoverfourdecades.IamalsoindebtedtoDr
Nina A. Nedolya for the painstaking correction of the manuscript and for
useful suggestions.
I dedicate this book to my wife Liesbeth who continuously supported me
during my career in chemistry.
L. Brandsma
June, 2003
This Page Intentionally Left Blank
Contents
Chapter 1 Procedures and Equipment
1.1 General................................................................. 1
1.2 Reactions in liquid ammonia..................................... 1
1.3 Some practical hints................................................ 3
Chapter 2 Preparation, Purification and Storage of Some
Solvents and Reagents
2.1 Solvents ................................................................ 11
2.2 Reagents ............................................................... 13
2.3 Experimental section................................................ 16
References........................................................................ 23
Chapter 3 Generation of Metallated Acetylenes, Allenes and Cumulenes
3.1 Deprotonation of acetylenes witha
terminal triple bond................................................. 25
3.2 Side reactions......................................................... 27
3.3 In situgeneration of metallatedacetylenes and
cumulenes by elimination reactions ............................ 28
3.4 1,3-Dimetallated acetylenes....................................... 30
3.5 Metallation of allenes and acetyleneswitha
non-terminal triplebond .......................................... 31
3.6 Addition oforganolithium compounds and
lithium alanate to compoundswith anenyne
ordiyne system ...................................................... 34
3.7 Formation of alkaliacetylides from acetylenes witha
non-terminal triplebondandfrom allenes by
the actionof strongbases......................................... 35
3.8 Generation of metallatedacetylenes bysuccessive
dehalogenations orbysuccessivedehydrohalogenation
and dehalogenation................................................. 36
3.9 Experimental section................................................ 38
3.10 Replacement of the lithiumbyothermetals and
application in synthesis............................................ 80
3.11 Solubilities of alkali acetylides................................... 81
References........................................................................ 81
Chapter 4 Reactions of Metallated Acetylenes and Allenes with
Alkylating Agents
4.1 Alkylation withalkyl halides..................................... 85
4.2 Reaction withoxiranesandoxetanes.......................... 88
vii
viii CONTENTS
4.3 Reaction of metallatedacetylenes andallenes
with(cid:2)-haloethers.................................................... 89
4.4 Reaction withorthoesters......................................... 90
4.5 Experimentalsection................................................ 90
References........................................................................ 117
Chapter 5 Reactions with Aldehydes and Ketones
5.1 Surveyof laboratorymethods................................... 119
5.2 Experimentalsection................................................ 121
References........................................................................ 133
Chapter 6 Carboxylation, Acylation and Related Reactions
6.1 Introduction........................................................... 135
6.2 Reactions withheterocumulenes ................................ 138
6.3 Acylation reactions.................................................. 139
6.4 Experimentalsection................................................ 142
References........................................................................ 158
Chapter 7 Silylation, Stannylation and Phosphorylation
7.1 Introduction........................................................... 161
7.2 Experimentalsection................................................ 162
References........................................................................ 173
Chapter 8 Sulphenylation and Related Reactions
8.1 Methods forthe direct introduction of sulphur,
seleniumand tellurium............................................. 175
8.2 Experimentalsection................................................ 177
References........................................................................ 188
Chapter 9 Halogenation of Acetylenes
9.1 Methods forthe direct introduction of halogen............ 191
9.2 Experimentalsection................................................ 192
References........................................................................ 202
Chapter 10 Acetylenes, Allenes and Cumulenes by Elimination Reactions
10.1 Surveyof methods .................................................. 203
10.2 Experimentalsection................................................ 206
References........................................................................ 227
Chapter 11 Cumulenes by Dehalogenation of Geminal
Dihalogenocyclopropanes
11.1 Introduction........................................................... 229
11.2 Experimentalsection................................................ 230
References........................................................................ 234
viii
CONTENTS ix
Chapter 12 Acetylenic and Allenic Derivatives by Substitution on
sp- and sp2-Carbon
12.1 Nucleophilic 1,1-substitution onsp-carbon.................. 235
12.2 Nucleophilic 1,3-substitution onsp- andsp2-carbon...... 236
12.3 Electrophilic 1,3-substitutions.................................... 237
12.4 Experimental section................................................ 241
References........................................................................ 264
Chapter 13 Aminoalkylation of Acetylenic Compounds
13.1 Introduction........................................................... 267
13.2 Experimental section................................................ 268
References........................................................................ 272
Chapter 14 Cross-coupling between 1-Alkynes and 1-Bromo-1-alkynes
14.1 Introduction........................................................... 273
14.2 Experimental section................................................ 276
References........................................................................ 279
Chapter 15 Copper Halide-Catalysed Oxidative Coupling of Acetylenes
15.1 Methods, scope andlimitations ................................. 281
15.2 Experimental section................................................ 283
References........................................................................ 291
Chapter 16 Transition Metals-Catalysed Couplings of Acetylenes
with sp2-Halides
16.1 Introduction........................................................... 293
16.2 Scopeand limitations .............................................. 294
16.3 Relative ratesof coupling......................................... 298
16.4 Regiochemistry....................................................... 299
16.5 Synthetic applicationsof the cross-couplingreactions
with acetylenes....................................................... 300
16.6 Practical aspects of the coupling reactions................... 301
16.7 Experimental section................................................ 304
References........................................................................ 317
Chapter 17 Base-Catalysed Isomerisations of Acetylenic Compounds
17.1 Introduction........................................................... 319
17.2 Experimental section................................................ 320
References........................................................................ 340
Chapter 18 Allenic Compounds by 2,3- and 3,3-Sigmatropic
Rearrangements
18.1 2,3-Sigmatropic rearrangements................................. 341