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	Volume 1

I	Synthesis of Allenes	1

1	Synthesis of Allenes by Isomerization Reactions A. Stephen K. Hashmi	3
1.1	Introduction	3
1.2	Prototropic Rearrangements and Related Reactions of Alkynes	6
1.2.1	Hydrogen Atoms or Alkyl Groups as Substituents	6
1.2.2	Alkenyl or Aryl Groups as Substituents	9
1.2.3	Alkinyl Groups as Substituents	12
1.2.4	Carbonyl Groups as Substituents	13
1.2.5	Halogens as Substituents	17
1.2.6	Oxygen as the Substituent	19
1.2.7	Nitrogen as the Substituent	21
1.2.8	Sulfur as the Substituent	23
1.2.9	Silyl and Stannyl Substituents	25
1.2.10	Phosphorus as the Substituent	26
1.2.11	Allenes from Prototropic Isomerizations of Alkynes as Reactive Intermediates	27
1.3	Sigmatropic Rearrangements	27
1.3.1	[2,3]-Sigmatropic Rearrangements	27
1.3.2	[3,3]-Sigmatropic Rearrangements	29
1.4	Rearrangements of Other Systems with at Least Two -Bonds	33
1.5	Retro-Ene Reactions	33
1.6	Electrocyclic Ring Openings	34
1.7	Intramolecular Conjugate Additions	34
1.8	Complex Reactions and Rearrangements	35
1.9	Conclusion	36
2	Metal-Mediated Synthesis of Allenes Anja Hoffmann-Röder and Norbert Krause	51
2.1	Introduction
2.2	Copper-Mediated Synthesis of Allenes	52
2.2.1	Substitution Reactions	52
2.2.2	Addition Reactions	61
2.3	Lithium-, Magnesium- and Zinc-Mediated Synthesis of Allenes	70
2.4	Aluminum- and Indium-Mediated Synthesis of Allenes	75
2.5	Titanium- and Samarium-Mediated Synthesis of Allenes	79
2.6	Conclusion	87
3	Transition Metal-Catalyzed Synthesis of Allenes Masamichi Ogasawara and Tamio Hayashi	93
3.1	Introduction	93
3.2	Formation of Allenes by Substitution Reactions	93
3.2.1	S_N2´ Substitution of Propargyl Compounds	93
3.2.2	S_N2´ Substitution of 2-Halo-1,3-Butadienes and Related Compounds	112
3.2.3	S_N2´ Substitution of Pent-2-en-4-ynyl Acetates	117
3.2.4	S_E2´ Substitution of Propargyl-Metal Species	118
3.3	Formation of Allenes by Addition Reactions	121
3.3.1	1,4-Addition to Conjugated Enynes and Related Reactions	121
3.3.2	1,6-Conjugate Addition to Enynylcarbonyl Compounds	128
3.4	Formation of Allenes by Elimination Reactions	129
3.5	Other Miscellaneous Methods of Preparing Allenes	131
3.6	Formation of 1,2,3-Butatrienes	133
3.7	Conclusion	136
4	Enantioselective Synthesis of Allenes Hiroaki Ohno, Yasuo Nagaoka, and Kiyoshi Tomioka	141
4.1	Introduction	141
4.2	Chirality Transfer from Propargylic Compounds	141
4.2.1	Organocopper-Mediated Alkylation of Propargyl Alcohol Derivatives	141
4.2.2	Copper-Mediated Halogenation of Propargyl Alcohol Derivatives	148
4.2.3	Rearrangement of Propargyl Alcohol Derivatives	152
4.2.4	Palladium(0)-Catalyzed Reactions of Propargyl Alcohol Derivatives	155
4.2.5	S_N2´ Reduction of Propargyl Alcohol Derivatives	158
4.2.6	Ring-Opening Reactions of Propargyl Epoxides and Related Compounds	160
4.2.7	Chiral Propargyl- or Allenyl-Metal Reagents	163
4.3	Elimination Reactions of Chiral Allylic Compounds	165
4.3.1	Chirality Transfer from Allylic Position	165
4.3.2	Elimination Reactions of Allylic Compounds Having a Chiral Leaving Group	168
4.4	Synthesis of Allenes Using Chiral Reagents	169
4.4.1	Asymmetric Deprotonation-Protonation	169
4.4.2	Asymmetric Horner-Wadsworth-Emmons and Related Reactions	171
4.5	Direct Asymmetric Synthesis of Allenes Using an External Chiral Catalyst	171
4.6	Synthesis of Allenes Using Internal Chiral Auxiliaries	175
4.7	Kinetic Resolution	175
4.8	Conclusion	177

II	Special Classes of Allenes	183

5	Allenic Hydrocarbons - Preparation and Use in Organic Synthesis Henning Hopf	185
5.1	Introduction	185
5.2	Allenic Hydrocarbons from Simple Building Blocks	186
5.3	Preparation of Allenic Hydrocarbons	188
5.3.1	General Methods	188
5.3.2	Alkylallenes	190
5.3.3	Vinylallenes	194
5.3.4	Ethynylallenes	197
5.3.5	Conjugated Bisallenes	199
5.3.6	Cyclopropylallenes	202
5.3.7	Arylallenes	204
5.3.8	Allenes Carrying Other Unsaturated Substituents	209
5.3.9	Semicyclic Allenic Hydrocarbons	217
5.4	Allenic Hydrocarbons as Reaction Intermediates	218
5.5	Why Allenic Hydrocarbons Are of Interest in Preparative Organic Chemistry	222
6	Cyclic Allenes Up to Seven-Membered Rings Manfred Christl	243
6.1	Introduction	243
6.2	Three-, Four- and Five-Membered Rings	245
6.3	Six-Membered Rings	248
6.3.1	Unsubstituted 1,2-Cyclohexadiene	248
6.3.2	Substituted 1,2-Cyclohexadienes	260
6.3.3	Bridged and Annulated 1,2-Cyclohexadienes	266
6.3.4	1,2,4-Cyclohexatriene, 3²-1H-Naphthalene and Their Derivatives	272
6.3.5	Heterocyclic Derivatives of 1,2,4-Cycloheptatriene (162) and 3²-1H-Naphthalene (221)	289
6.3.6	Heterocyclic Derivatives of 1,2-Cyclohexadiene (6)	299
6.4	Seven-Membered Rings	324
6.4.1	1,2-Cycloheptadiene and Its Simple Derivatives	325
6.4.2	1,2,4,6-Cycloheptatetraene and Its Simple Derivatives	332
6.4.3	Annulated and Bridged Derivatives of 1,2-Cycloheptadiene	349
6.4.4	Heterocyclic Derivatives of 1,2-Cycloheptadiene	350
7	Acceptor-Substituted Allenes Klaus Banert and Jens Lehmann	359
7.1	Introduction	359
7.2	Synthesis of Acceptor-Substituted Allenes	360
7.2.1	Methods with Building Up of the Carbon Skeleton of the Allene	360
7.2.2	Prototropic Isomerization of Propargyl Compounds	361
7.2.3	[2,3]-Sigmatropic Rearrangement of Propargyl Compounds	364
7.2.4	Other Rearrangement Reactions	367
7.2.5	Nucleophilic Substitution of Propargyl Compounds	369
7.2.6	Palladium-Catalyzed Carbonylation of Propargyl Compounds	371
7.2.7	1,4-Addition to Enynes	373
7.2.8	Elimination and Cleavage Reactions	373
7.2.9	Introduction of the Acceptor Substituent into the Allene	375
7.2.10	Synthesis from Other Acceptor-Substituted Allenes	378
7.3	Reactions of Acceptor-Substituted Allenes	379
7.3.1	Nucleophilic Addition	379
7.3.2	Nucleophilic Addition Including Ring Closure	386
7.3.3	Electrophilic Addition	390
7.3.4	Ring Closure to Form Carbocycles	392
7.3.5	Ring Closure to Produce Heterocycles	395
7.3.6	Diels-Alder Reactions	401
7.3.7	Other Cycloaddition Reactions	406
7.3.8	Sigmatropic Rearrangement Reactions	411
7.3.9	Other Rearrangement Reactions	414
7.3.10	Miscellaneous Reactions	415
7.4	Conclusion	416
8	Donor-Substituted Allenes Reinhold Zimmer and Hans-Ulrich Reissig	425
8.1	Introduction	425
8.2	O-Substituted Allenes	427
8.2.1	Synthesis of O-Substituted Allenes	427
8.2.2	Deprotonation of Alkoxyallenes and Reaction with Electrophiles - Ring-Closing Reactions	431
8.2.3	Cycloadditions and Cyclizations	449
8.2.4	Formation of Acetals and Subsequent Metathesis Reactions	458
8.2.5	Miscellaneous Reactions of O-Substituted Allenes	462
8.3	N-Substituted Allenes	467
8.3.1	Synthesis of N-Substituted Allenes	467
8.3.2	Reactions of N-Substituted Allenes	471
8.4	S- and Se-Substituted Allenes	475
8.4.1	Synthesis of S-Substituted Allenes	475
8.4.2	Reactions of S-Substituted Allenes	478
8.4.3	Synthesis and Reactions of Se-Substituted Allenes	484
8.5	Conclusion	485
9	Synthesis and Reactions of Allenylmetal Compounds James A. Marshall, Benjamin W. Gung_, and Melissa L. Grachan	493
9.1	Introduction	493
9.1.1	Preparation	493
9.1.2	Reaction Characteristics	494
9.2	Allenyllithium Reagents	497
9.2.1	Structure	497
9.2.2	Regioselectivity of Silylation	500
9.3	Allenylcopper Reagents	508
9.4	Allenylmagnesium Halides	509
9.5	Allenylboron Reagents	510
9.6	Allenyltitanium Reagents	517
9.7	Allenylsilanes	527
9.8	Allenylstannanes	543
9.8.1	Allenyltin Halide Reagents	543
9.8.2	Trialkylallenyltin Reagents	546
9.8.3	Reactions of Chiral Allenyltin Reagents	548
9.8.4	Synthesis and Reactions of Chiral Allenyltin Halides	551
9.8.5	Chiral Catalysis	554
9.8.6	Oxygenated Allenyltin Halides	555
9.8.7	Intramolecular Additions	556
9.9	Allenylpalladium Reagents	558
9.9.1	Synthesis	558
9.9.2	Cross-Coupling Reactions	559
9.9.3	Decarboxylation	561
9.9.4	Carbonylation	562
9.9.5	Cyclizations and Cascade Reactions	563
9.10	Allenylzinc Reagents	565
9.10.1	Racemic Allenylzinc Reagents	566
9.10.2	Enantioenriched Chiral Allenylzinc Reagents	568
9.11	Allenylindium Reagents	574
9.11.1	Metal-Halogen Exchange	576
9.11.2	Chiral Lewis Acids	584
9.12	Miscellaneous Allenylmetal Reagents	585


	Volume 2

III	Reactions of Allenes	593

10	Ionic Additions to Allenes Shengming Ma	595
10.1	Unfunctionalized Allenes	595
10.1.1	Electrophilic Additions	595
10.1.2	Nucleophilic Additions	603
10.2	Allenylsilanes	604
10.2.1	Electrophilic Additions	604
10.3	1,2-Allenyl Sulfides	608
10.4	1,2-Allenyl Ethers	609
10.4.1	Electrophilic Additions	609
10.4.2	Nucleophilic Additions	613
10.5	1,2-Allenyl Halides	614
10.5.1	Electrophilic Additions	614
10.5.2	Nucleophilic Additions	615
10.6	Phosphorus-Containing Allenes	619
10.6.1	Electrophilic Addition	619
10.6.2	Nucleophilic Addition	621
10.7	1,2-Allenyl Sulfoxides	626
10.7.1	Electrophilic Additions	626
10.7.2	Nucleophilic Additions	626
10.8	1,2-Allenyl Sulfones	629
10.8.1	Electrophilic Additions	629
10.8.2	Nucleophilic Additions	630
10.9	Allenylamines	638
10.9.1	Electrophilic Additions	638
10.9.2	Nucleophilic Additions	647
10.10	2,3-Allenols	650
10.10.1	Electrophilic Additions	650
10.10.2	Nucleophilic Additions	654
10.11	1,2-Allenic Ketones	659
10.11.1	Electrophilic Additions	659
10.11.2	Nucleophilic Additions	661
10.12	2,3-Allenoic Acids and 2,3-Allenoates	667
10.12.1	Electrophilic Additions	667
10.12.2	Nucleophilic Additions	669
10.13	2,3-Allenamides	680
10.13.1	Electrophilic Additions	680
10.13.2	Nucleophilic Additions	681
10.14	2,3-Allenyl Nitriles	683
10.14.1	Electrophilic Additions	683
10.14.2	Nucleophilic Additions	684
11	Fundamentals and Application of Free Radical Addition to Allenes Jens Hartung and Thomas Kopf	701
11.1	Introduction	701
11.2	Basic Principles	702
11.2.1	FMO Analysis of 1,2-Dienes	702
11.2.2	Radical Addition to the Cumulated -System in Allenes	703
11.3	Intermolecular Additions of Alkyl Radicals to Allenes	712
11.3.1	Conclusion	716
11.4	Intramolecular Radical Additions to Cumulated Double Bonds	716
11.4.1	Cyclizations on to the Central Carbon Atoms of Allenes	717
11.4.2	Cyclizations via Radical Addition to C	720
11.4.3	Conclusion	723
11.5	Summary and Perspectives	724
12	Cycloadditions of Allenes Masahiro Murakami and Takanori Matsuda	727
12.1	Introduction	727
12.2	[2 + 2]-Cycloaddition of Allenes	727
12.2.1	Dimerization of Allenes	727
12.2.2	Cycloaddition with Olefins	733
12.2.3	Photocycloaddition with Ketones and Aldehydes	743
12.2.4	Cycloaddition with Ketenes	743
12.2.5	Cycloaddition with Isocyanates	746
12.2.6	Cycloaddition with Other X=Y Bonds	747
12.2.7	Cycloaddition with Alkynes	749
12.3	[3 + 2]-Cycloaddition of Allenes	750
12.3.1	Cycloaddition with Nitrones	750
12.3.2	Cycloaddition with Nitrile Oxides	754
12.3.3	Cycloaddition with Diazo Compounds	756
12.3.4	Cycloaddition with Azides	758
12.3.5	Cycloaddition with Other 1,3-Dipoles	759
12.4	[4 + 2]-Cycloaddition of Allenes	760
12.4.1	Intermolecular Cycloaddition of Activated Allenes	760
12.4.2	Intramolecular Cycloaddition of Activated Allenes	773
12.4.3	Fluoroallenes	777
12.4.4	Alkoxyallenes	778
12.4.5	Cycloaddition of Strained Cyclic Allenes	784
12.4.6	Cycloaddition of Unactivated Allenes	785
12.4.7	Hetero-Diels-Alder Reaction	787
12.5	Vinylallenes and Bisallenes	791
12.5.1	Intermolecular [4 + 2]-Cycloaddition of Vinylallenes	791
12.5.2	Intramolecular [4 + 2]-Cycloaddition of Vinylallenes	797
12.5.3	[4 + 2]-Cycloaddition of Bisallenes	800
12.6	Miscellaneous Cycloaddition Reaction of Allenes	802
12.6.1	[5 + 2]-Cycloaddition of Allenes	802
12.6.2	Cycloaddition of Allenes with Tropones	803
12.6.3	[3 + 2]-Cycloaddition of Allenylsilanes	804
12.6.4	Phosphine-Catalyzed Cycloaddition of Allenes	806
12.6.5	[4 + 2]-Cycloaddition of N-Allenylsulfonamides Involving a 1,3-Sulfonyl Shift	809
13	Cyclizations of Allenes Marcus A. Tius	817
13.1	Introduction	817
13.2	Nazarov and Related Reactions	817
13.3	Annulations Making Use of Trialkylsilyl Allenes (Danheiser Reactions)	829
13.4	Allene Cyclizations Leading to Dihydrofurans, Furans, Pyrrolines and Pyrroles	834
13.5	Ene Reactions of Allenes	839
13.6	Miscellaneous Cyclizations of Allenes	841
13.7	Conclusion	843
14	Transition Metal-Catalyzed Cross-Couplings of Allenes Reinhold Zimmer and Hans-Ulrich Reissig	847
14.1	Introduction	847
14.2	Cross-Coupling Reactions of Allenes Producing Compounds with an Intact 1,2-Diene Moiety	849
14.2.1	Cross-Coupling Reactions of Allenyl Halides	849
14.2.2	Cross-Coupling Reactions of Allenylmetal Compounds	856
14.2.3	Cross-Coupling Reactions of -Substituted Allenes	860
14.3	Cross-Coupling Reactions of Allenes at the Central Position	862
14.4	Synthesis of Alkynes	870
14.5	Miscellaneous Reactions	872
14.6	Conclusion	873
15	Transition Metal-Catalyzed Cycloisomerizations of Allenes A. Stephen K. Hashmi	877
15.1	Introduction	877
15.2	Alcohols as Nucleophiles	881
15.3	Allenyl Ketones	889
15.4	Allenic Carboxylic Acids	895
15.5	Amines as Nucleophiles	897
15.6	Amides as Nucleophiles	902
15.7	Sulfonamides as Nucleophiles	904
15.8	Imines and Related Groups as Nucleophiles	905
15.9	Oximes as Nucleophiles	907
15.10	Phosphonic Acids	908
15.11	Activated C-H Bonds	909
15.12	Reaction with Other C-C Multiple Bonds	910
15.13	Conclusion	918
16	Transition Metal-Catalyzed Addition/Cycloaddition of Allenes Tadakatsu Mandai	925
16.1	Introduction	925
16.2	Reactions via Carbopalladation	925
16.3	Carbonylation	937
16.4	Pauson-Khand Reactions	942
16.5	Carbon-Metal Bond Formation	946
16.6	Allenic Alder Ene Reaction and Cycloisomerization	953
16.7	Homo- and Cross-Coupling Reactions	965
16.8	Miscellaneous Reactions	968
16.9	Conclusions	970
17	Oxidation of Allenes Attila Horváth and Jan-E. Bäckvall	973
17.1	Introduction	973
17.2	Palladium(II)-Catalyzed 1,2-Oxidations	973
17.2.1	Dihalogenation	976
17.2.2	Oxybromination	977
17.2.3	Bromolactonization	978
17.2.4	Bromoamidation	979
17.2.5	Cyclization-Dimerization of -Allenyl Acids and Ketones	981
17.2.6	Cyclization of Alkenyl- and Dienylallenes	982
17.3	Catalytic Osmylation	983
17.4	Ruthenium-Catalyzed Oxidation	984
17.5	Epoxidation	985
17.5.1	Epoxidation and Subsequent Intermolecular Ring Opening	985
17.5.2	Epoxidation and Subsequent Intramolecular Ring Opening	986
17.5.3	Epoxidation and Subsequent Ring Opening with Rearrangement	991
17.6	Oxidation by Sulfur	992

IV	Applications	995

18	Allenic Natural Products and Pharmaceuticals Norbert Krause and Anja Hoffmann-Röder	997
18.1	Introduction	997
18.2	Allenic Natural Products	999
18.2.1	Linear Allenes	999
18.2.2	Carotinoids and Terpenoids	1003
18.2.3	Bromoallenes	1010
18.2.4	Other Naturally Occurring Allenes and Cumulenes	1015
18.3	Pharmacologically Active Allenes	1018
18.3.1	Steroids	1019
18.3.2	Prostaglandins and Carbacyclins	1021
18.3.3	Amino Acids	1025
18.3.4	Nucleoside Analogs	1028
18.3.5	Other Pharmacologically Active Allenes	1031
18.4	Conclusion	1032
19	Allenes in Natural Product Synthesis Kay M. Brummond and Hongfeng Chen	1041
19.1	Introduction	1041
19.2	Cycloaddition Reactions	1041
19.2.1	[2 + 2]-Cycloaddition Reactions	1042
19.2.2	[4 + 2]-Cycloadditions	1046
19.2.3	[5 + 2]-Cycloaddition Reactions	1057
19.3	Transition Metal-Catalyzed Cycloadditions	1058
19.4	Transition Metal-Promoted Heterocyclizations	1064
19.5	Acid-Catalyzed Rearrangements	1069
19.6	Allenyl Organometallic Intermediates	1073
19.7	Allenoates	1080
19.8	Imino-Ene Reactions	1081
19.9	Oxidation of Allenes	1083
19.10	Electrocyclizations	1086
19.11	Miscellaneous	1086
20	Enyne-Allenes Kung K. Wang	1091
20.1	Introduction	1091
20.2	Synthesis and Cyclization	1092
20.2.1	Rearrangement of Enediynyl Propargylic Diazenes	1092
20.2.2	Condensation Between Allenic Aldehydes and [-(Trialkylsilyl)allenyl]boranes	1094
20.2.3	Palladium-Catalyzed Cross-Coupling Reactions	1096
20.2.4	The Horner-Wittig and Related Reactions	1099
20.2.5	Prototropic Rearrangement	1103
20.2.6	Phosphorus- and Sulfur-Substituted Enyne-Allenes	1106
20.2.7	Chlorinated Enyne-Allenes	1110
20.2.8	[3,3]-Sigmatropic Rearrangements	1111
20.2.9	Nucleophilic Substitution with Rearrangement of Propargylic Derivatives	1113
20.2.10	Nucleophilic Addition to Conjugated Systems	1115
20.2.11	Rearrangement of 4-Alkynyl-4-hydroxy-3-methylenecyclobutenes	1116
20.2.12	Hydrolytic Decarboxylation of -Alkynylmalonates and -Alkynylacetic Acids	1117
20.2.13	Enyne-Allenes Having a Keto or an Aldehydic Substituent at the Allenic Terminus	1118
20.3	Cascade Radical Cyclizations of Biradicals Generated from Enyne-Allenes	1119
20.4	Synthesis of a C₄₄H₂₆ Hydrocarbon Having a Carbon Framework Represented on the Surface of C₆₀	1122
20.5	Synthesis of Twisted 4,5-Diarylphenanthrenes	1122
20.6	Synthesis of the Benzo[b]fluorene Core of the Kinamycins	1123
	Subject Index	1127

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