Modern Allene Chemistry, 2 Volume Set

by Krause, Norbert; Hashmi, A. Stephen K.

• ISBN13: 9783527306718
• ISBN10: 3527306714
• Edition: 1st
• Format: Hardcover
• Copyright: 2004-12-10
• Publisher: Wiley-VCH

Summary

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.

Author Biography

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 Znrich) 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).<br> <br> 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 Gnnter 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.

Table of Contents

I Synthesis of Allenes	1	(182)
Synthesis of Allenes by Isomerization Reactions	3	(48)
A. Stephen K. Hashmi
Introduction	3	(3)
Prototropic Rearrangements and Related Reactions of Alkynes	6	(21)
Hydrogen Atoms or Alkyl Groups as Substituents	6	(3)
Alkenyl or Aryl Groups as Substituents	9	(3)
Alkinyl Groups as Substituents	12	(1)
Carbonyl Groups as Substituents	13	(4)
Halogens as Substituents	17	(2)
Oxygen as the Substituent	19	(2)
Nitrogen as the Substituent	21	(2)
Sulfur as the Substituent	23	(2)
Silyl and Stannyl Substituents	25	(1)
Phosphorus as the Substituent	26	(1)
Allenes from Prototropic Isomerizations of Alkynes as Reactive Intermediates	27	(1)
Sigmatropic Rearrangements	27	(6)
[2,3]-Sigmatropic Rearrangements	27	(2)
[3,3]-Sigmatropic Rearrangements	29	(4)
Rearrangements of Other Systems with at Least Two π-Bonds	33	(1)
Retro-Ene Reactions	33	(1)
Electrocyclic Ring Openings	34	(1)
Intramolecular Conjugate Additions	34	(1)
Complex Reactions and Rearrangements	35	(1)
Conclusion	36	(15)
Metal-Mediated Synthesis of Allenes	51	(42)
Anja Hoffmann-Roder
Norbert Krause
Introduction
Copper-Mediated Synthesis of Allenes	52	(18)
Substitution Reactions	52	(9)
Addition Reactions	61	(9)
Lithium-, Magnesium- and Zinc-Mediated Synthesis of Allenes	70	(5)
Aluminum- and Indium-Mediated Synthesis of Allenes	75	(4)
Titanium- and Samarium-Mediated Synthesis of Allenes	79	(8)
Conclusion	87	(6)
Transition Metal-Catalyzed Synthesis of Allenes	93	(48)
Masamichi Ogasawara
Tamio Hayashi
Introduction	93	(1)
Formation of Allenes by Substitution Reactions	93	(28)
SN2' Substitution of Propargyl Compounds	93	(19)
SN2' Substitution of 2-Halo-1,3-Butadienes and Related Compounds	112	(5)
SN2' Substitution of Pent-2-en-4-ynyl Acetates	117	(1)
SE2' Substitution of Propargyl-Metal Species	118	(3)
Formation of Allenes by Addition Reactions	121	(8)
1,4-Addition to Conjugated Enynes and Related Reactions	121	(7)
1,6-Conjugate Addition to Enynylcarbonyl Compounds	128	(1)
Formation of Allenes by Elimination Reactions	129	(2)
Other Miscellaneous Methods of Preparing Allenes	131	(2)
Formation of 1,2,3-Butatrienes	133	(3)
Conclusion	136	(5)
Enantioselective Synthesis of Allenes	141	(42)
Hiroaki Ohno
Yasuo Nagaoka
Kiyoshi Tomioka
Introduction	141	(1)
Chirality Transfer from Propargylic Compounds	141	(24)
Organocopper-Mediated Alkylation of Propargyl Alcohol Derivatives	141	(7)
Copper-Mediated Halogenation of Propargyl Alcohol Derivatives	148	(4)
Rearrangement of Propargyl Alcohol Derivatives	152	(3)
Palladium(0)-Catalyzed Reactions of Propargyl Alcohol Derivatives	155	(3)
SN2' Reduction of Propargyl Alcohol Derivatives	158	(2)
Ring-Opening Reactions of Propargyl Epoxides and Related Compounds	160	(3)
Chiral Propargyl-- or Allenyl--Metal Reagents	163	(2)
Elimination Reactions of Chiral Allylic Compounds	165	(4)
Chirality Transfer from Allylic Position	165	(3)
Elimination Reactions of Allylic Compounds Having a Chiral Leaving Group	168	(1)
Synthesis of Allenes Using Chiral Reagents	169	(2)
Asymmetric Deprotonation--Protonation	169	(2)
Asymmetric Horner--Wadsworth--Emmons and Related Reactions	171	(1)
Direct Asymmetric Synthesis of Allenes Using an External Chiral Catalyst	171	(4)
Synthesis of Allenes Using Internal Chiral Auxiliaries	175	(1)
Kinetic Resolution	175	(2)
Conclusion	177	(6)
II Special Classes of Allenes	183	(410)
Allenic Hydrocarbons -- Preparation and Use in Organic Synthesis	185	(58)
Henning Hopf
Introduction	185	(1)
Allenic Hydrocarbons from Simple Building Blocks	186	(2)
Preparation of Allenic Hydrocarbons	188	(30)
General Methods	188	(2)
Alkylallenes	190	(4)
Vinylallenes	194	(3)
Ethynylallenes	197	(2)
Conjugated Bisallenes	199	(3)
Cyclopropylallenes	202	(2)
Arylallenes	204	(5)
Allenes Carrying Other Unsaturated Substituents	209	(8)
Semicyclic Allenic Hydrocarbons	217	(1)
Allenic Hydrocarbons as Reaction Intermediates	218	(4)
Why Allenic Hydrocarbons Are of Interest in Preparative Organic Chemistry	222	(21)
Cyclic Allenes Up to Seven-Membered Rings	243	(116)
Manfred Christl
Introduction	243	(2)
Three-, Four- and Five-Membered Rings	245	(3)
Six-Membered Rings	248	(76)
Unsubstituted 1,2-Cyclohexadiene	248	(12)
Substituted 1,2-Cyclohexadienes	260	(6)
Bridged and Annulated 1,2-Cyclohexadienes	266	(6)
1,2,4-Cyclohexatriene, 3δ2-1H-Naphthalene and Their Derivatives	272	(17)
Heterocyclic Derivatives of 1,2,4-Cycloheptatriene (162) and 3δ2-1H-Naphthalene (221)	289	(10)
Heterocyclic Derivatives of 1,2-Cyclohexadiene (6)	299	(25)
Seven-Membered Rings	324	(35)
1,2-Cycloheptadiene and Its Simple Derivatives	325	(7)
1,2,4,6-Cycloheptatetraene and Its Simple Derivatives	332	(17)
Annulated and Bridged Derivatives of 1,2-Cycloheptadiene	349	(1)
Heterocyclic Derivatives of 1,2-Cycloheptadiene	350	(9)
Acceptor-Substituted Allenes	359	(66)
Klaus Banert
Jens Lehmann
Introduction	359	(1)
Synthesis of Acceptor-Substituted Allenes	360	(19)
Methods with Building Up of the Carbon Skeleton of the Allene	360	(1)
Prototropic Isomerization of Propargyl Compounds	361	(3)
[2,3]-Sigmatropic Rearrangement of Propargyl Compounds	364	(3)
Other Rearrangement Reactions	367	(2)
Nucleophilic Substitution of Propargyl Compounds	369	(2)
Palladium-Catalyzed Carbonylation of Propargyl Compounds	371	(2)
1,4-Addition to Enynes	373	(1)
Elimination and Cleavage Reactions	373	(2)
Introduction of the Acceptor Substituent into the Allene	375	(3)
Synthesis from Other Acceptor-Substituted Allenes	378	(1)
Reactions of Acceptor-Substituted Allenes	379	(37)
Nucleophilic Addition	379	(7)
Nucleophilic Addition Including Ring Closure	386	(4)
Electrophilic Addition	390	(2)
Ring Closure to Form Carbocycles	392	(3)
Ring Closure to Produce Heterocycles	395	(6)
Diels--Alder Reactions	401	(5)
Other Cycloaddition Reactions	406	(5)
Sigmatropic Rearrangement Reactions	411	(3)
Other Rearrangement Reactions	414	(1)
Miscellaneous Reactions	415	(1)
Conclusion	416	(9)
Donor-Substituted Allenes	425	(68)
Reinhold Zimmer
Hans-Ulrich Reissig
Introduction	425	(2)
O-Substituted Allenes	427	(40)
Synthesis of O-Substituted Allenes	427	(4)
Deprotonation of Alkoxyallenes and Reaction with Electrophiles -- Ring-Closing Reactions	431	(18)
Cycloadditions and Cyclizations	449	(9)
Formation of Acetals and Subsequent Metathesis Reactions	458	(4)
Miscellaneous Reactions of O-Substituted Allenes	462	(5)
N-Substituted Allenes	467	(8)
Synthesis of N-Substituted Allenes	467	(4)
Reactions of N-Substituted Allenes	471	(4)
S- and Se-Substituted Allenes	475	(10)
Synthesis of S-Substituted Allenes	475	(3)
Reactions of S-Substituted Allenes	478	(6)
Synthesis and Reactions of Se-Substituted Allenes	484	(1)
Conclusion	485	(8)
Synthesis and Reactions of Allenylmetal Compounds	493	(100)
James A. Marshall
Benjamin W. Gung
Melissa L. Grachan
Introduction	493	(4)
Preparation	493	(1)
Reaction Characteristics	494	(3)
Allenyllithium Reagents	497	(11)
Structure	497	(3)
Regioselectivity of Silylation	500	(8)
Allenylcopper Reagents	508	(1)
Allenylmagnesium Halides	509	(1)
Allenylboron Reagents	510	(7)
Allenyltitanium Reagents	517	(10)
Allenylsilanes	527	(16)
Allenylstannanes	543	(15)
Allenyltin Halide Reagents	543	(3)
Trialkylallenyltin Reagents	546	(2)
Reactions of Chiral Allenyltin Reagents	548	(3)
Synthesis and Reactions of Chiral Allenyltin Halides	551	(3)
Chiral Catalysis	554	(1)
Oxygenated Allenyltin Halides	555	(1)
Intramolecular Additions	556	(2)
Allenylpalladium Reagents	558	(7)
Synthesis	558	(1)
Cross-Coupling Reactions	559	(2)
Decarboxylation	561	(1)
Carbonylation	562	(1)
Cyclizations and Cascade Reactions	563	(2)
Allenylzinc Reagents	565	(9)
Racemic Allenylzinc Reagents	566	(2)
Enantioenriched Chiral Allenylzinc Reagents	568	(6)
Allenylindium Reagents	574	(11)
Metal--Halogen Exchange	576	(8)
Chiral Lewis Acids	584	(1)
Miscellaneous Allenylmetal Reagents	585	(8)
III Reactions of Allenes	593	(402)
Ionic Additions to Allenes	595	(106)
Shengming Ma
Fundamentals and Application of Free Radical Addition to Allenes	701	(26)
Jens Hartung
Thomas Kopf
Cycloadditions of Allenes	727	(90)
Masahiro Murakami
Takanori Matsuda
Cyclizations of Allenes	817	(30)
Marcus A. Tius
Transition Metal-Catalyzed Cross-Couplings of Allenes	847	(30)
Reinhold Zimmer
Hans-Ulrich Reissig
Transition Metal-Catalyzed Cycloisomerizations of Allenes	877	(48)
A. Stephen K. Hashmi
Transition Metal-Catalyzed Addition/Cycloaddition of Allenes	925	(48)
Tadakatsu Mandai
Oxidation of Allenes	973	(22)
Attila Horvath
Jan-E. Backvall
IV Applications	995	(132)
Allenic Natural Products and Pharmaceuticals	997	(44)
Norbert Krause
Anja Hoffmann-Roder
Allenes in Natural Product Synthesis	1041	(50)
Kay M. Brummond
Hongfeng Chen
Enyne-Allenes	1091	(36)
Kung K. Wang
Subject Index	1127