Methods and Applications of Cycloaddition Reactions in Organic Syntheses

Nagatoshi Nishiwaki

• Publisher: Wiley
• Year: 2013
• Print ISBN: 9781118299883
• eBook ISBN: 9781118778203
• Edition: 1
• Topic: Ciencias físicas
• Subtopic: Química

Advanced tools for developing new functional materials and applications in chemical research, pharmaceuticals, and materials science

Cycloadditions are among the most useful tools for organic chemists, enabling them to build carbocyclic and heterocyclic structures. These structures can then be used to develop a broad range of functional materials, including pharmaceuticals, agrochemicals, dyes, and optics. With contributions from an international team of leading experts and pioneers in cycloaddition chemistry, this book brings together and reviews recent advances, trends, and emerging research in the field.

Methods and Applications of Cycloaddition Reactions in Organic Syntheses focuses on two component cycloadditions, with chapters covering such topics as:

• N1 unit transfer reaction to C–C double bonds
• [3+2] Cycloaddition of ?, ?-unsaturated metal-carbene complexes
• Formal [3+3] cycloaddition approach to natural product synthesis
• Development of new methods for the construction of heterocycles based on cycloaddition reaction of 1,3-dipoles
• Cycloreversion approach for preparation of large ?-conjugated compounds
• Transition metal-catalyzed or mediated [5+1] cycloadditions

Readers will learn methods for seamlessly executing important reactions such as Diels-Alder and stereoselective dipolar reactions in order to fabricate heterocyclic compounds, natural products, and functional molecules. The book not only features cutting-edge topics, but also important background information, such as the contributors' process for developing new methodologies, to help novices become fully adept in the field. References at the end of each chapter lead to original research papers and reviews for facilitating further investigation of individual topics.

Covering the state of the science and technology, Methods and Applications of Cycloaddition Reactions in Organic Syntheses enables synthetic organic chemists to advance their research and develop new functional materials and applications in chemical research, pharmaceuticals, and materials science.

1

[2+1]-Type Cyclopropanation Reactions

Akio Kamimura

Yamaguchi University, Ube, Yamaguchi, Japan

1.1 Introduction

1.2 Cyclopropanation Reaction via Michael-Induced Ring Closure Reaction

1.2.1 Introduction

1.2.2 Halo-Substituted Nucleophiles in MIRC Reaction

1.2.3 Ylides for Cyclopropanation

1.3 Simmons–Smith Cyclopropanation and Related Reactions

1.3.1 Introduction

1.3.2 The Simmons–Smith Reaction with Zinc Reagents

1.4 Diazoalkanes with Transition Metal Catalysts

1.4.1 Introduction

1.4.2 Rhodium-Catalyzed Reactions

1.4.3 Copper-Catalyzed Reactions

1.4.4 Ruthenium-Catalyzed Reactions

1.4.5 Cobalt- and Iron-Catalyzed Reactions

1.4.6 Other Transition Metal-Catalyzed Reactions

1.4.7 Cyclopropanation Without Transition Metal Catalysts

1.4.8 Cyclopropanation of Dihalocarbenes

1.5 Cycloisomerization with Transition Metal Catalysts

1.5.1 Introduction

1.5.2 Gold Complex-Catalyzed Reactions

1.5.3 Palladium Complex-Catalyzed Reactions

1.5.4 Platinum Complex-Catalyzed Reactions

1.5.5 Ruthenium Complex-Catalyzed Reactions

1.5.6 Other Metal Complex-Catalyzed Reactions

1.6 Kulinkovich Reactions

1.6.1 Introduction

1.6.2 The Kulinkovich Reaction to Esters, Ketones, and Amides

1.6.3 Kulinkovich Reaction to Nitriles

1.6.4 Other Ti-Mediated Cyclopropanation Reactions

1.7 Miscellaneous [2+1]-Type of Cyclopropanation Reactions

References

1.1 Introduction

Cyclopropane is often present in natural and biologically active products. Alternatively, the cyclopropane structure has been used as parts for the modification of such products. It has a high ring strain because of its bond angle, and this property facilitates unique reactions. The formation of cyclopropanes has been the focus of considerable study and many reviews are available [1]. Among the methods reported in these reviews, [2+1]-type cycloaddition by carbenoids is a representative strategy [2]. In this chapter, we collected recent representative examples of [2+1]-type cyclopropanation reactions. We reviewed and classified the literature from the past decade into six categories: Michael-induced ring closure (MIRC), the Simmons–Smith reaction, reactions by carbenes from diazoalkanes catalyzed/noncatalyzed by transition metals, cycloisomerization reactions by transition metal catalysts, the Kulinkovich reaction, and miscellaneous reactions. Since this chapter focuses on [2+1]-type cycloaddition, we excluded γ-elimination-type cyclopropanations from a single molecule. The asymmetric synthesis of cyclopropanes, which is a topic of interest among synthetic chemists, is discussed in each category. Although we carefully reviewed the literature, it could be possible we may have missed some citations owing to the significant amount of related studies.

1.2 Cyclopropanation Reaction Via Michael-Induced Ring Closure Reaction

1.2.1 Introduction

Cyclopropanes are prepared by the nucleophilic attack on electron-deficient alkenes followed by intramolecular nucleophilic substitution. This occurs when the nucleophile or electron-deficient alkene contains a leaving group at an appropriate position. This type of reaction is called the MIRC [3] and is frequently employed for cyclopropanation. There are two types of MIRC reactions, which are expressed by Equations 1.1 and 1.2.

(1.1)

(1.2)

Equation 1.1 shows an MIRC reaction with an electron-drawing alkene containing a leaving group, which reacts with a nucleophile that is generated under reaction conditions. In this case, all carbons in cyclopropane originate from the alkene. Equation 1.2 is an MIRC reaction with a nucleophile containing a leaving group. Cyclopropane formed in this sequence contains two carbons from the alkene and one carbon from the nucleophile. Because this chapter focuses on [2+1] cycloaddition, we will concentrate on the latter case of MIRC cyclopropanation.

The leaving group is typically halogen if the nucleophile is der...

Table of contents

• Cover
• Title Page
• Copyright
• Preface
• Contributors
• Part I: [2+1] Cycloaddition
• Part II: [2+2] Cycloaddition
• Part III: [2+2] and [4+2]/[2+2] Cycloaddition
• Part IV: [3+2] Cycloaddition
• Part V: [3+2], [3+3], and [4+2] Cycloaddition
• Part VI: [3+2] and [5+1] Cycloaddition
• Part VII: [3+3] Cycloaddition
• Part VIII: [4+2] Cycloaddition
• Part IX: [4+2]/[3+2] Cycloaddition
• Part X: [5+1] Cycloaddition
• Part XI: [4+3] Cycloaddition
• Part XII: [5+2] Cycloaddition
• Index