Organic Reactions, Volume 100

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• Publisher: Wiley
• Year: 2019
• Print ISBN:
  9781119456667
• eBook ISBN:
  9781119570394
• Edition: 1
• Topic: Physical Sciences
• Subtopic: Organic Chemistry

Written by a "who is who" of leading organic chemists, this anniversary volume represent the Organic Reactions editors' choice of the most important, ground-breaking and versatile reactions in current organic synthesis. The 15 reaction types selected for this volume include reactions for carbon-carbon bond formation, cross-coupling reactions, hydro- and halofunctionalizations, among many others.
In line with the successful recipe of the series, each chapter is focused on a single reaction, discussing its mechanism and stereochemistry, scope and limitations, applications to synthesis, comparison with other methods, and experimental procedures. Each chapter concludes with a tabular survey of selected key application examples, complete with reported reaction conditions and yields, to serve as a quick reference guide for synthesis planning.

CHAPTER 1
THE NEGISHI CROSS‐COUPLING REACTION

Colin Diner and Michael G. Organ

Center for Catalysis Research and Innovation (CCRI), Department of Chemistry and Biomolecular Sciences, 30 Marie‐Curie, Ottawa, Ontario, Canada, KIN 6N5

CONTENTS

1. Acknowledgements
2. Introduction
3. Mechanism and Stereochemistry
   1. Features of Palladium‐Catalyzed Reactions
   2. Effect of Additives and Solvents in Palladium‐Catalyzed Reactions
   3. Features of Nickel‐Catalyzed Reactions
   4. C(sp²) Coupling Partners
      1. Configurational Specificity of Alkenyl Electrophiles
   5. C(sp³) Coupling Partners
      1. Constitutional Site Selectivity of Secondary Alkylzinc Reagents
      2. Configurational Stability of Secondary Alkylzinc Reagents
4. Scope and Limitations
   1. The Organozinc Reagents
      1. Alkylzinc Reagents
         1. Enantiospecific Cross‐Coupling Reactions of Alkyl Nucleophiles
         2. Enantioselective Cross‐Coupling Reactions of Alkyl Nucleophiles
      2. Alkenylzinc Reagents
      3. Alkynylzinc Reagents
      4. Aryl‐ and Heteroarylzinc Reagents
         1. Enantioselective Approaches Towards Chiral Biaryls
   2. The Electrophile
      1. Alkyl Electrophiles
         1. Enantiospecific Cross‐Coupling Reactions of Alkyl Electrophiles
         2. Enantioselective Cross‐Coupling Reactions of Alkyl Electrophiles
         3. Desymmetrizing Cross‐Coupling Reactions of meso‐Anhydrides
         4. Cross‐Coupling Reactions of Allylic Electrophiles
      2. Alkenyl Electrophiles
      3. Alkynyl Electrophiles
      4. Aryl and Heteroaryl Electrophiles
      5. Acyl Electrophiles
5. Applications to Synthesis
   1. Overview
      1. Tetrapetalone A‐Me Aglycon.141
      2. Dehydromicrosclerodermin B
      3. (–)‐Daphenylline
      4. Negishi Cross‐Coupling in Flow
      5. Multi‐kg C(sp²)–C(sp³) Coupling
6. Comparison With Other Methods
7. Experimental Conditions
   1. Preparation of Organozinc Reagents
      1. Transmetalation
      2. Oxidative Addition of Zn into Organohalides
      3. Cobalt Catalysis
      4. Direct Zinc‐Halogen Exchange
      5. Direct Zincation of (Hetero)arenes
      6. Synthesis of Bench‐Stable Organozinc Pivalates
   2. Reaction Conditions
      1. Catalysts
      2. Solvents
      3. Additives
8. Experimental Procedures
   1. 1. (S)‐N‐(Boc)‐Allylglycine Methyl Ester [Direct Insertion of Activated Zinc into an Alkyl Iodide and Cross‐Coupling with an Alkenyl Bromide].157
      2. (S)‐2‐(1‐Cyclohexylbutan‐2‐yl)naphthalene [Stereospecific Cross‐Coupling of an Alkylzinc Reagent with an Enantioenriched Electrophile].15
      3. tert‐Butyl 2,2,4‐Trimethyl‐5‐octadecyloxazolidine‐3‐carboxylate [Sequential One‐Pot Chemoselective C(sp³)–C(sp³) Cross‐Coupling of a Bifunctional α,ω‐Bromochloroalkane].50
      4. 5‐Methyl‐2,2′‐bipyridine [Lithium–Halogen Exchange and Transmetalation for the Cross‐Coupling of a Heteroaromatic Compound].158
9. Tabular Survey

Acknowledgements

We are very grateful for the instruction and counsel of Prof. Steven Weinreb throughout the process of drafting this chapter. Dr. Danielle Soenen and Dr. Linda Press were also instrumental in aiding us in the formatting and polishing of the text, tables, and imagery throughout this text.

Introduction

Since its inception in 1977, the Negishi cross‐coupling reaction has had a profound impact on organic synthesis.¹ The reaction unites two organic fragments, an organic (pseudo)halide and an organozinc reagent to make a new C–C bond with the elimination of a zinc salt (Scheme 1). The utility of the reaction in linking unsaturated fragments through transition‐metal catalysts lik...

Table of contents

• COVER
• TABLE OF CONTENTS
• “C”
• INTRODUCTION TO THE SERIES ROGER ADAMS, 1942
• INTRODUCTION TO THE SERIES SCOTT E. DENMARK, 2008
• PREFACE FOR VOLUME 100
• CHAPTER 1: THE NEGISHI CROSS‐COUPLING REACTION
• CHAPTER 2: GENERATION AND TRAPPING OF FUNCTIONALIZED ARYL‐ AND HETEROARYLMAGNESIUM AND ‐ZINC COMPOUNDS
• CHAPTER 3: Copper‐Catalyzed, Enantioselective Hydrofunctionalization of Alkenes
• CHAPTER 4: The Catalytic, Enantioselective Favorskii Reaction: in Situ Formation of Metal Alkynylides and Their Additions to Aldehydes
• CHAPTER 5: ENANTIOSELECTIVE LITHIATION–SUBSTITUTION OF NITROGEN‐CONTAINING HETEROCYCLES
• CHAPTER 6: CATALYTIC, ENANTIOSELECTIVE, TRANSFER HYDROGENATION
• CHAPTER 7: HYDROFUNCTIONALIZATION OF ALKENES BY HYDROGEN‐ATOM TRANSFER
• CHAPTER 8: CARBON–CARBON BOND FORMATION BY METALLAPHOTOREDOX CATALYSIS
• CHAPTER 9: SUZUKI–MIYAURA CROSS‐COUPLING
• CHAPTER 10: ‐DIRECTED C–H ALKYLATION OF SUBSTITUTED BENZENES
• CHAPTER 11: CATALYTIC, ENANTIOSELECTIVE, C–H FUNCTIONALIZATION TO FORM CARBON–CARBON BONDS
• CHAPTER 12: CATALYTIC, ENANTIOSELECTIVE FLUORINATION REACTIONS
• CHAPTER 13: CATALYST‐CONTROLLED GLYCOSYLATION
• CHAPTER 14: PALLADIUM‐CATALYZED AMINATION OF ARYL HALIDES
• CHAPTER 15: CATALYTIC, ENANTIOSELECTIVE, COPPER–BORYL ADDITIONS TO ALKENES
• CUMULATIVE CHAPTER TITLES BY VOLUME
• AUTHOR INDEX, VOLUMES 1-100
• CHAPTER AND TOPIC INDEX, VOLUMES 1–100
• END USER LICENSE AGREEMENT