The Claisen Rearrangement: Methods and Applications

The first comprehensive coverage of all facets of the Claisen rearrangement and its variants, presenting catalytic, enzymatic and theoretic aspects. As such, this book helps synthetic chemists to exploit the vast potential of this elegant C–C linking reaction, discusses a wealth of catalytic options, and gives those more theory–minded chemists a detailed insight into the mechanistic aspects of the Claisen rearrangement. The result is an invaluable source of information and a ready reference helping every organic chemist to find the best solution for their particular Claisen rearrangement problem.
From the Contents:Chorismate Mutase–Catalyzed Claisen RearrangementChiral Metal Complex–Catalyzed Aliphatic Claisen RearrangementAlphabetic and Aromatic Claisen RearrangementMetal–Catalyzed Claisen RearrangementSimple Enolate and Chelate Enolate Claisen RearrangementClaisen–Johnson Orthoester RearrangementThe Meerwein–Eschenmoser Claisen RearrangementThe Carroll RearrangementThio–Claisen RearrangementAza–Claisen Rearrangement
A must–have for all organic and catalytic chemists, as well as those working with/on organometallics, and in industry.

Spis treści:
Preface.
List of Contributors.
1 Chorismate–Mutase–Catalyzed Claisen Rearrangement (Hong Guo and Niny Rao).
1.1 Introduction.
1.2 Experimental Studies.
1.3 Catalytic Mechanism of Chorismate Mutase.
1.4 Conclusion.
2 Chiral–Metal–Complex–Catalyzed Aliphatic Claisen Rearrangement (Koichi Mikami and Katsuhiro Akiyama).
2.1 Introduction.
2.2 Binding Modes of Main–group and Late Transition Metals.
2.3 Aluminum(III)–promoted Claisen Rearrangement.
2.4 Copper(II)–catalyzed Claisen Rearrangement.
2.5 Palladium(II)–catalyzed Claisen Rearrangement.
3 Alip hatic and Aromatic Claisen Rearrangement.
3.1 Aliphatic Claisen Rearrangement (Hayato Ichikawa and Keiji Maruoka).
3.1.1 Introduction.
3.1.2 Synthesis of Allyl Vinyl Ethers.
3.1.3 Acyclic Aliphatic Claisen Rearrangement.
3.1.4 Claisen Rearrangement of Cyclic Allyl Vinyl Ethers.
3.1.5 Cyclic Vinyl Ethers.
3.1.6 Cyclic Allyl Ethers.
3.1.7 Tandem Reactions Including Aliphatic Claisen Rearrangement.
3.1.8 The Carbanion–Accelerated Claisen Rearrangement.
3.1.9 Conclusion.
3.2 Aromatic Claisen Rearrangement (Hisanaka Ito and Takeo Taguchi).
3.2.1 Introduction.
3.2.2 Mechanism.
3.2.3 Substrate and Substituent Effect.
3.2.4 Reaction Conditions.
3.2.5 Thio–, Amino–, and Related Claisen Rearrangement.
3.2.6 Asymmetric Synthesis.
3.2.7 Synthetic Applications.
4 The Ireland–Claisen Rearrangement (1972–2004) (Christopher M. McFarland and Matthias C. McIntosh).
4.1 Introduction.
4.2 History.
4.3 Numbering and Nomenclature.
4.4 Rearrangement Temperature, Substituent Effects and Catalysis.
4.5 Transition State Structure.
4.6 Stereochemical Aspects.
4.7 Methods of Ketene Acetal Formation.
4.8 Structural Variations in Allylic Esters.
4.9 Applications to Natural Product Synthesis.
4.10 Propargyl Esters.
4.11 Conclusion.
5 Simple and Chelate Enolate Claisen Rearrangement.
5.1 Simple Enolate Claisen Rearrangement (Mukund G. Kulkarni).
5.1.1 Introduction.
5.1.2 History.
5.1.3 Simple Enolates of Allylic Esters.
5.1.4 Stereoselectivity in Enolate Formation.
5.1.5 Simple Enolates of Allylic Esters of a–Hetero Acids.
5.1.6 Simple Enolates of N–Allyl Amides.
5.1.7 Miscellaneous Enolates.
5.1.8 Conclusion.
5.2 Chelate Enolate Claisen Rearrangement (Uli Kazmaier).
5.2.1 Introduction.
5.2.2 Claisen Rearrangements of Substrates with Chelating Substituents in the a–Position.
5.2.3 Claisen Rearrangements of Substrates Bearing Chelating Substituents in the β–Position.
5.2.4 Chelation Controlled Aza–Claisen Rearrangements.
6 Claisen–Johnson Orthoester Rearrangement (Yves Langlois).
6.1 Introduction.
6.2 Historical Overview.
6.3 Mechanistic Aspects.
6.4 Synthetic Applications.
6.5 Conclusion.
7 The Meerwein–Eschenmoser–Claisen Rearrangement (Stefan N. Gradl and Dirk Trauner).
7.1 Definition, Discovery and Scope.
7.2 Formation of Ketene N,O–Acetals.
7.3 Selectivity.
7.4 Applications in Synthesis.
8 The Carroll Rearrangement (Mark A. Hatcher and Gary H. Posner).
8.1 Introduction.
8.2 Mechanism.
8.3 Synthetic Applications.
8.4 Carroll Variants.
8.5 Conclusion.
9 Thio–Claisen Rearrangement (Stéphane Perrio, Vincent Reboul, Carole Alayrac, and Patrick Metzner).
9.1 Introduction.
9.2 Basic Versions.
9.3 Rearrangement with Stereochemical Control.
9.4 Applications in Organic Synthesis.
9.5 Conclusion.
10 Aza–Claisen Rearrangement (Udo Nubbemeyer).
10.1 Introduction.
10.2 Aromatic Simple Aza–Claisen Rearrangements.
10.3 Aliphatic Simple Aza–Claisen Rearrangements.
10.4 Amide Acetal and Amide Enolate Claisen Rearrangements.
10.5 Zwitterionic Aza–Claisen Rearrangements.
10.6 Alkyne Aza–Claisen Rearrangements.
10.7 Iminoketene Claisen Rearrangements.
11 Mechanistic Aspects of the Aliphatic Claisen Rearrangement (Julia Rehbein and Martin Hiersemann).
References.
Subject Index.

Nota biograficzna:
Martin Hiersemann was born 1966 in Berlin, Germany. He received his Ph.D. in 1995 under the guidance of Johann Mulzer at the Freie Universitat Berlin. After postdoctoral stay with Gary A. Molander at the University of Colorado, he started his independent research at the Dresden University of Technology in the fall of 1997. He was a visiting scientist at the University of Tsukuba in the group of Akira Hosomi in 2002, at Harvard University in the group of David A. Evans in 2003 and at the Montana State University with Paul A. Grieco in 2004. His research activities are concerned with the catalysis of sigmatropic rearrangements as well as natural product synthesis.
Udo Nubbemeyer received his Diploma and PhD in the group of Prof. Dr. E. Winterfeldt (University of Hannover) and spent a postdoctoral spell at the Ciba–Geigy Laboratory at the University of Fribourg (Switzerland) with Prof. D. Bellus and Dr. B. Ernst (1989/1990). From 1991 to 1996, he worked on his ′Habilitation′ in the group of Prof. Dr. J. Mulzer (Freie Universitat Berlin). Then, he passed an assistant lecturer period in Berlin and a temporary professorship at the TU Dresden (1999/2001). Actually, he works as an associate professor at the Johannes Gutenberg–Universitat of Mainz. His major topics of interest are olefin synthesis, aza Claisen rearrangements, radical cyclizations, medium–sized rings, total synthesis of natural and pharmaceutically important products, alkaloids, eicosanoids, steroids, and amino acids.

Okładka tylna:
The first comprehensive coverage of all facets of the Claisen rearrangement and its variants, presenting catalytic, enzymatic and theoretic aspects. As such, this book helps synthetic chemists to exploit the vast potential of this elegant C–C linking reaction, discusses a wealth of catalytic options, and gives those more theory–minded chemists a detailed insight into the mechanistic aspects of the Claisen rearrangement. The result is an invaluable source of information and a ready reference helping every organic chemist to find the best solution for their particular Claisen rearrangement problem.
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