Rearrangements with Migration to Electrophilic Heteroatomic Centers
Timeless Classics in Organic Synthesis
- 1st Edition - October 9, 2024
- Imprint: Elsevier
- Author: Sosale Chandrasekhar
- Language: English
- Paperback ISBN:9 7 8 - 0 - 1 2 - 8 2 3 7 4 3 - 4
- eBook ISBN:9 7 8 - 0 - 1 2 - 8 2 3 7 4 4 - 1
Rearrangements with Migration to Electrophilic Heteroatomic Centers: Timeless Classics in Organic Synthesis covers the basic principles and synthetic applications of a critic… Read more
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Request a sales quoteRearrangements with Migration to Electrophilic Heteroatomic Centers: Timeless Classics in Organic Synthesis covers the basic principles and synthetic applications of a critically important class of organic reactions that date back to the founding period of organic chemistry. These reactions are not only of historical and pedagogical interest, but also have great practical value to this day, being inevitable in any strategy concerning the introduction of nitrogen and oxygen functionality. The book is made up of three parts, dealing with the Beckmann reaction, the Hoffmann family of reactions and the Baeyer-Villiger reaction.The book strikes a balance between delineation and exhaustiveness, with up-to-date refences for readers requiring in-depth coverage. Relevant industrial applications, including pharmaceutical processes, are included.
- Summarizes mechanistic background with an emphasis on synthetic applications
- Includes up-to-date references that allow for locating original papers for experimental procedures
- Provides applications in the synthesis of complex molecules and natural products to judge the scope and limitations of each reaction
Senior undergraduate students and researchers, including both academic and industrial researchers engaged in organic synthesis. Pharmaceutical chemists, particularly those engaged in process development
- Title of Book
- Cover image
- Title page
- Table of Contents
- Disclaimer
- Copyright
- Dedication
- Foreword
- Preface
- Chapter 1. Introduction
- General comments
- Historical background
- The molecular structural theory
- Organic chemistry‒‒The beginnings
- Rearrangement reactions via migrations to electron-deficient centers
- Baeyer–Villiger, Beckmann, and Hofmann reactions
- The Baeyer–Villiger reaction
- The Beckmann reaction
- The Hofmann family of reactions (including Curtius and Lossen variants)
- The Hofmann reaction
- The Curtius reaction
- The Lossen reaction
- Summarizing comments
- Chapter 2. The Baeyer–Villiger reaction
- Introduction
- Discussion
- Mechanistic background: Scope and stereochemistry
- The Criegee mechanism
- General remarks
- Isotope effects, linear free energy relationships and the rate-determining step
- Exceptions: Rate-determining addition, concerted and free radical mechanisms
- Stereoelectronic effects: The ever-evolving Criegee mechanism
- General background
- Studies with conformationally restricted models
- Significance of stereoelectronic effects as the key to further developments
- Synthetic investigations
- Earlier studies—General comments
- Oxidants, migratory aptitudes, and chemoselectivity
- The Baeyer–Villiger oxidation: A survey by type of carbonyl compound
- Oxidations of acyclic ketones2,4
- Oxidations of cyclic ketones
- Oxidations of aldehydes and dicarbonyl compounds; the Dakin reaction
- Oxidations of aryl ketones
- Oxidations of α,β-unsaturated ketones and aldehydes
- Remote substituent effects
- Asymmetric synthesis via Baeyer–Villiger oxidations
- General background
- Resolution and desymmetrization: Principles; a quasi-kinetic analysis; reactivity versus selectivity
- PKR: Dichotomous definitions; role of catalyst (PKR vs. CKR); general precedent
- Examples of CKR, PKR, and desymmetrization
- Miscellany: Quasi Baeyer–Villiger reactions; ionic liquids as media; nonconventional conditions
- Quasi Baeyer–Villger oxidations of carbonyl derivatives (acetals, ketals, oximes, etc.)
- Baeyer–Villiger reactions in ionic liquids
- Other nonconventional conditions
- Enzyme-catalyzed Baeyer–Villiger reactions
- General remarks; monooxygenases and perhydrolases
- Kinetic resolutions with enzyme-catalyzed Baeyer–Villiger reactions
- “Designer enzymes” by directed evolution: Protein engineering and site-directed mutagenesis
- “Designer” Baeyer–Villiger monooxygenases
- The Baeyer–Villiger reaction in biosynthesis
- Miscellaneous reactions and commercial applications
- Summarizing comments
- Chapter 3. The Beckmann reactions
- Introduction
- General background
- The Beckmann family of reactions and its three variants
- Discussion
- Mechanistic background
- Stereochemical aspects of the Beckmann reaction
- Synthetic applications: General comments
- Reagents and catalysts for the Beckmann reaction: Past and present
- Synthetic applications: Early work and broad scope
- Synthetic applications: Ketoximes
- Synthetic applications: Aldoximes
- Synthetic applications: Fragmentations (“abnormal Beckmann reaction”)
- Synthetic applications: Nucleophilic capture of the nitrilium ion intermediate; cyclizations
- Novel techniques and exotic variants
- The Beckmann reaction in complex syntheses
- Summarizing comments
- Chapter 4. The Hofmann and related rearrangements
- Chapter 4A. The Hofmann rearrangement
- Introduction
- Discussion
- General background
- Methodological considerations: Alkaline, acidic, and neutral variants
- Mechanistic and stereochemical considerations
- Recent developments: Hypervalent iodine–based reagents
- Select examples and case studies
- Summarizing comments
- Chapter 4B. The Curtius rearrangement
- Introduction
- Discussion
- General background
- Methodological considerations: Broad overview
- Mechanistic and stereochemical background
- Recent developments: Diphenylphosphoryl azide; the Shioiri reagent and the modified Curtius reaction
- Select examples and case studies
- Innovative techniques employed for the Curtius rearrangement: Flow systems and solid-phase reactions
- Unusual and exotic variations of the Curtius rearrangement: Aza-Curtius and phosphinoyl Curtius reactions; a remarkable asymmetric synthesis
- Applications of the Curtius rearrangement: As tactical methodology
- Applications of the Curtius rearrangement: As part of complex synthesis strategy
- Summarizing comments
- Chapter 4C. The Schmidt rearrangements
- Introduction
- Discussion
- General background
- Methodological considerations
- Summarizing comments
- Chapter 4D. The Lossen rearrangement
- Introduction
- Discussion
- General background
- Mechanistic and methodological considerations
- Modern developments and improved procedures for the Lossen reaction
- Nonactivated hydroxamic acids, N-hydroxyimides, chiral versions, and exotic phosphorus analogs
- Stereoelectronic effects in the Lossen rearrangement
- Applications of the Lossen rearrangement
- Summarizing comments
- Index
- Edition: 1
- Published: October 9, 2024
- Imprint: Elsevier
- No. of pages: 300
- Language: English
- Paperback ISBN: 9780128237434
- eBook ISBN: 9780128237441
SC
Sosale Chandrasekhar
Sosale Chandrasekhar was born on 25 April 1952; he earned his MSc from IIT Bombay, his PhD from the University of London, and his Postdoc from Cambridge University, Max-Planck Institute and Muelheim/Ruhr, University of Montreal. He taught at Indian Institute of Science Bangalore since 1984, and as Professor from 2003 onwards, and retired in 2017. His research interests include synthetic and mechanistic organic chemistry, stereochemistry and biological applications.
Affiliations and expertise
Professor, Department of Organic Chemistry, Indian Institute of Science, Bangalore, Karnataka, IndiaRead Rearrangements with Migration to Electrophilic Heteroatomic Centers on ScienceDirect