In this two-volume handbook, the editors Norbert Krause and A. Stephen K. Hashmi present all the important aspects and facts related to this hot topic. The treatment covers the whole range from the synthesis and classification, via reactions, right up to possible applications in the synthesis of natural products and drugs. With their excellent contributions, an international team of outstanding authors highlight the multifarious uses and classes of allenes, making this an indispensable work for every organic chemist.
Table of Contents
Volume 1.I Synthesis of Allenes.1 Synthesis of Allenes by Isomerization Reactions (A. Stephen K. Hashmi).1.1 Introduction.1.2 Prototropic Rearrangements and Related Reactions of Alkynes.1.3 Sigmatropic Rearrangements.1.4 Rearrangements of Other Systems with at Least Two p-Bonds.1.5 Retro-Ene Reactions.1.6 Electrocyclic Ring Openings.1.7 Intramolecular Conjugate Additions.1.8 Complex Reactions and Rearrangements.1.9 Conclusion.2 Metal-Mediated Synthesis of Allenes (Anja Hoffmann-Roder and Norbert Krause).2.1 Introduction.2.2 Copper-Mediated Synthesis of Allenes.2.3 Lithium-, Magnesium- and Zinc-Mediated Synthesis of Allenes.2.4 Aluminum- and Indium-Mediated Synthesis of Allenes.2.5 Titanium- and Samarium-Mediated Synthesis of Allenes.2.6 Conclusion.3 Transition Metal-Catalyzed Synthesis of Allenes (Masamichi Ogasawara and Tamio Hayashi).3.1 Introduction.3.2 Formation of Allenes by Substitution Reactions.3.3 Formation of Allenes by Addition Reactions.3.4 Formation of Allenes by Elimination Reactions.3.5 Other Miscellaneous Methods of Preparing Allenes.3.6 Formation of 1,2,3-Butatrienes.3.7 Conclusion.4 Enantioselective Synthesis of Allenes (Hiroaki Ohno, Yasuo Nagaoka, and Kiyoshi Tomioka).4.1 Introduction.4.2 Chirality Transfer from Propargylic Compounds.4.3 Elimination Reactions of Chiral Allylic Compounds.4.4 Synthesis of Allenes Using Chiral Reagents.4.5 Direct Asymmetric Synthesis of Allenes Using an External Chiral Catalyst.4.6 Synthesis of Allenes Using Internal Chiral Auxiliaries.4.7 Kinetic Resolution.4.8 Conclusion.II Special Classes of Allenes.5 Allenic Hydrocarbons - Preparation and Use in Organic Synthesis (Henning Hopf).5.1 Introduction.5.2 Allenic Hydrocarbons from Simple Building Blocks.5.3 Preparation of Allenic Hydrocarbons.5.4 Allenic Hydrocarbons as Reaction Intermediates.5.5 Why Allenic Hydrocarbons Are of Interest in Preparative Organic Chemistry.6 Cyclic Allenes Up to Seven-Membered Rings (Manfred Christl).6.1 Introduction.6.2 Three-, Four- and Five-Membered Rings.6.3 Six-Membered Rings.6.4 Seven-Membered Rings.7 Acceptor-Substituted Allenes (Klaus Banert and Jens Lehmann).7.1 Introduction.7.2 Synthesis of Acceptor-Substituted Allenes.7.3 Reactions of Acceptor-Substituted Allenes.7.4 Conclusion.8 Donor-Substituted Allenes (Reinhold Zimmer and Hans-Ulrich Reissig).8.1 Introduction.8.2 O-Substituted Allenes.8.3 N-Substituted Allenes.8.4 S- and Se-Substituted Allenes.8.5 Conclusion.9 Synthesis and Reactions of Allenylmetal Compounds (James A. Marshall, Benjamin W. Gung, and Melissa L. Grachan).9.1 Introduction.9.2 Allenyllithium Reagents.9.2.1 Structure.9.3 Allenylcopper Reagents.9.4 Allenylmagnesium Halides.9.5 Allenylboron Reagents.9.6 Allenyltitanium Reagents.9.7 Allenylsilanes.9.8 Allenylstannanes.9.9 Allenylpalladium Reagents.9.10 Allenylzinc Reagents.9.11 Allenylindium Reagents.9.12 Miscellaneous Allenylmetal Reagents.Volume 2.III Reactions of Allenes.10 Ionic Additions to Allenes (Shengming Ma).10.1 Unfunctionalized Allenes.10.2 Allenylsilanes.10.3 1,2-Allenyl Sulfides.10.4 1,2-Allenyl Ethers.10.5 1,2-Allenyl Halides.10.6 Phosphorus-Containing Allenes.10.7 1,2-Allenyl Sulfoxides.10.8 1,2-Allenyl Sulfones.10.9 Allenylamines.10.10 2,3-Allenols.10.11 1,2-Allenic Ketones.10.12 2,3-Allenoic Acids and 2,3-Allenoates.10.13 2,3-Allenamides.10.14 2,3-Allenyl Nitriles.11 Fundamentals and Application of Free Radical Addition to Allenes (Jens Hartung and Thomas Kopf).11.1 Introduction.11.2 Basic Principles.11.3 Intermolecular Additions of Alkyl Radicals to Allenes,11.4 Intramolecular Radical Additions to Cumulated Double Bonds,11.5 Summary and Perspectives.12 Cycloadditions of Allenes (Masahiro Murakami and Takanori Matsuda).12.1 Introduction.12.2 [2 + 2]-Cycloaddition of Allenes.12.3 [3 + 2]-Cycloaddition of Allenes.12.4 [4 + 2]-Cycloaddition of Allenes.12.5 Vinylallenes and Bisallenes.12.6 Miscellaneous Cycloaddition Reaction of Allenes.13 Cyclizations of Allenes (Marcus A. Tius).13.1 Introduction.13.2 Nazarov and Related Reactions.13.3 Annulations Making Use of Trialkylsilyl Allenes (Danheiser Reactions).13.4 Allene Cyclizations Leading to Dihydrofurans, Furans, Pyrrolines and Pyrroles.13.5 Ene Reactions of Allenes.13.6 Miscellaneous Cyclizations of Allenes.13.7 Conclusion.14 Transition Metal-Catalyzed Cross-Couplings of Allenes (Reinhold Zimmer and Hans-Ulrich Reissig).14.1 Introduction.14.2 Cross-Coupling Reactions of Allenes Producing Compounds with an Intact 1,2-Diene Moiety.14.3 Cross-Coupling Reactions of Allenes at the Central Position.14.4 Synthesis of Alkynes.14.5 Miscellaneous Reactions.14.6 Conclusion.15 Transition Metal-Catalyzed Cycloisomerizations of Allenes (A. Stephen K. Hashmi).15.1 Introduction.15.2 Alcohols as Nucleophiles.15.3 Allenyl Ketones.15.4 Allenic Carboxylic Acids.15.5 Amines as Nucleophiles.15.6 Amides as Nucleophiles.15.7 Sulfonamides as Nucleophiles.15.8 Imines and Related Groups as Nucleophiles.15.9 Oximes as Nucleophiles.15.10 Phosphonic Acids.15.11 Activated C-H Bonds.15.12 Reaction with Other C-C Multiple Bonds.15.13 Conclusion.16 Transition Metal-Catalyzed Addition/Cycloaddition of Allenes (Tadakatsu Mandai).16.1 Introduction.16.2 Reactions via Carbopalladation.16.3 Carbonylation.16.4 Pauson-Khand Reactions.16.5 Carbon-Metal Bond Formation.16.6 Allenic Alder Ene Reaction and Cycloisomerization.16.7 Homo- and Cross-Coupling Reactions.16.8 Miscellaneous Reactions.16.9 Conclusions.17 Oxidation of Allenes (Attila Horvath and Jan-E. Backvall).17.1 Introduction.17.2 Palladium(II)-Catalyzed 1,2-Oxidations.17.3 Catalytic Osmylation.17.4 Ruthenium-Catalyzed Oxidation.17.5 Epoxidation.17.6 Oxidation by Sulfur.IV Applications.18 Allenic Natural Products and Pharmaceuticals (Norbert Krause and Anja Hoffmann-Roder)18.1 Introduction.18.2 Allenic Natural Products.18.3 Pharmacologically Active Allenes.18.4 Conclusion.19 Allenes in Natural Product Synthesis (Kay M. Brummond and Hongfeng Chen).19.1 Introduction.19.2 Cycloaddition Reactions.19.3 Transition Metal-Catalyzed Cycloadditions.19.4 Transition Metal-Promoted Heterocyclizations.19.5 Acid-Catalyzed Rearrangements.19.6 Allenyl Organometallic Intermediates.19.7 Allenoates.19.8 Imino-Ene Reactions.19.9 Oxidation of Allenes.19.10 Electrocyclizations.19.11 Miscellaneous.20 Enyne-Allenes (Kung K. Wang).20.1 Introduction.20.2 Synthesis and Cyclization.20.3 Cascade Radical Cyclizations of Biradicals Generated from Enyne-Allenes.20.4 Synthesis of a C44H26 Hydrocarbon Having a Carbon Framework Represented on the Surface of C60.20.5 Synthesis of Twisted 4,5-Diarylphenanthrenes.20.6 Synthesis of the Benzo[b]fluorene Core of the Kinamycins.Subject Index.
Norbert Krause, born in 1959, obtained his PhD in chemistry in 1986 under H. Hopf at the Technical University of Braunschweig. After postdoctoral appointments with D. Seebach (ETH Zurich) and M. Saunders (Yale University), he obtained his qualification in the group led by K. Hafner at the Technical University of Darmstadt in 1993. He was appointed to the University of Bonn in 1994 and subsequently moved to become Professor of Organic Chemistry at the University of Dortmund in 1998. He has received several awards, including the ADUC annual award for lecturers (1993), a Heisenberg scholarship (1994), and a JSPS Fellowship (2003). A. Stephen K. Hashmi is Professor for Organic Chemistry at Stuttgart University. Born in Munich, Germany, he completed his studies at the LMU Munich, gaining his doctorate under the supervision of Gunter Szeimies. During his post-doctorate at Stanford University, he worked with Barry M. Trost. His further postdoctoral work at the FU Berlin, Vienna University and Frankfurt University with Johann Mulzer and further activities at the University of Tasmania and Marburg University culminated in his position at Stuttgart University in 2001.