Organic Mechanisms. Xiaoping Sun

of Congress Cataloging‐in‐Publication Data Names: Sun, Xiaoping, 1960– author. Title: Organic mechanisms : reactions, methodology, and biological applications / Xiaoping Sun, University of Charleston, Charleston, West Virginia. Description: Second edition. | Hoboken, NJ : Wiley, 2021. | Includes index. Identifiers: LCCN 2020020410 (print) | LCCN 2020020411 (ebook) | ISBN 9781119618829 (cloth) | ISBN 9781119618843 (adobe pdf) | ISBN 9781119618867 (epub) Subjects: LCSH: Organic reaction mechanisms. Classification: LCC QD502.5 .S86 2021 (print) | LCC QD502.5 (ebook) | DDC 547/.139–dc23 LC record available at https://lccn.loc.gov/2020020410 LC ebook record available at https://lccn.loc.gov/2020020411

      Cover image: Light against rippled background (Digital) © Chad Baker/Getty Images, Organic mechanism diagram Courtesy of Xiaoping Sun

      Cover design by Wiley

      PREFACE

      The first edition of this book, Organic Mechanisms: Reactions, Methodology, and Biological Applications, was published in July 2013. In January 2019, Mr. Jonathan Rose, Senior Editor of Wiley in Hoboken, New Jersey, asked me to consider writing the second edition of the book. We both realized that because 6 years had passed since the publication of the first edition, it would be necessary to update the book with a new addition to meet the increasing needs for various upper‐level college students, instructors, and practicing chemists. I came up with a detailed proposal regarding how to modify the book and what new information will be added to the second edition. The proposal received very favorable peer reviews and was approved by Wiley in March 2019. Then I started writing the new edition. It took me 11 months to finish writing the second edition of the book. Meanwhile, I was teaching full‐time as well.

      Since 1998, I have been on faculty at two higher educational institutions, West Virginia University Institute of Technology (1998–2001) and University of Charleston (2001–present). My current and previous research interests have much emphasis on reaction mechanisms. When I teach upper‐level organic chemistry and biochemistry courses, the lectures are also strongly mechanisms based. In the past 20 years or so, my teaching and research have been reinforcing each other. Now, I wish to share my experiences with other colleagues, students, and different scientific workers in the chemical community by publishing the second edition of this book. Much new information, particularly many more new examples of biological applications and green chemistry methodology which encompass important organic reaction mechanisms, has been included in the updated edition.

The second edition of the book consists of 10 chapters. It starts with reviews of various fundamental physicochemical principles (Chapter 1), which are essential for studying organic mechanisms. General principles of green chemistry methods and enzymatic catalysis have been added to Chapter 1 in the new edition. Then, each of the following chapters is devoted to one major class of organic reactions. Thorough discussions on various reaction mechanisms are presented in the book in a very good detail, and a sophisticated and readily understandable manner. Special attention has been paid to mechanisms of different organic functionalization processes, such as methodology of aliphatic CH bond activation and functionalization, charge‐transfer aromatic nitration and recently developed chemistry of aromatic compounds, and cycloaddition of alkenes to 1,3‐dipolar‐like molecules. Substantial efforts have been made in demonstrating direct applications of organic mechanisms in elucidating sophisticated biological and biochemical processes and designing organic synthesis. This can be seen throughout all the chapters and reflects a remarkable feature of the book. In the second edition, many new examples of cycloaddition reactions, including those conducted in water representing green chemistry methodology, have been added in Chapter 4. Some new electrophilic aromatic substitution reactions developed in the recent 10 years or so have been added in Chapter 5. More biological applications in enzymatic reactions involving key organic mechanisms have been added in Chapters 6 and 8. Chapter 7 (Eliminations) has been essentially rewritten to cover many more interesting and challenging elimination reaction mechanisms and applications.

      To facilitate teaching and learning, a Solutions Manual and PowerPoint slides of all the figures will be provided by the author and will be available for professors on the book’s page on www.wiley.com\go\Sun\OrgMech_2e. I greatly appreciate all the constructive comments given by peer‐reviewers. The reviewers' comments have helped the author tremendously in improving the book.

      I would like to take this opportunity to dedicate my book to Dr. Jack Passmore, my former PhD supervisor, and to my organic chemistry and biochemistry students at University of Charleston. The book is also dedicated to my wife Cindy and my son Oliver.

      Xiaoping Sun, PhD

      Professor of Chemistry Charleston, West Virginia June 2020

      FIRST EDITION PREFACE

      In Summer 2010, I was contacted by Mr. Jonathan Rose, a senior editor of Wiley in Hoboken, New Jersey, for book review and possibly writing an organic mechanisms‐based textbook. We both agreed that a new book in this subject will meet the increasing needs of various upper‐level college students, instructors, and practicing chemists. I took up the challenge and came up with a detailed proposal regarding the contents, style, and features of the book. The proposal received favorable peer reviews and was approved by Wiley in December 2010. Then I started the writing process. It took me 18 months to finish writing the book. Meanwhile, I was teaching full‐time as well.

      Since 1998, I have been on faculty at two higher educational institutions, West Virginia University Institute of Technology (1998–2001) and University of Charleston (2001–present). My current and previous research interests have much emphasis on reaction mechanisms. When I teach upper‐level organic chemistry and biochemistry courses, the lectures are also strongly mechanisms based. In the past dozen years or so, my teaching and research have been reinforcing each other. Now I wish to share my experiences with other colleagues, students, and different scientific workers in the chemical community by publishing this book.

The book consists of 10 chapters. It starts with reviews of various fundamental physicochemical principles (Chapter 1) which are essential for studying organic mechanisms. Then each of the following chapters is devoted to one major class of organic reactions. Thorough discussions on various reaction mechanisms are presented in the book in a very good detail, and a sophisticated and readily understandable manner. Special attention has been paid to mechanisms of different organic functionalization processes, such as methodology of aliphatic C—H bond activation and functionalization, charge‐transfer aromatic nitration and recently developed chemistry of aromatic compounds, and cycloaddition of alkenes to 1,3‐dipolar‐like molecules. Substantial efforts have been made in demonstrating direct applications of organic mechanisms in elucidating sophisticated biological and biochemical processes and designing organic synthesis. This can be seen throughout all the chapters and reflects a remarkable feature of the book. To facilitate teaching and learning, a Solutions Manual and PowerPoint slides of all the figures will be provided by the author and will be available for professors on a companion website for adopting instructors. I greatly appreciate all the constructive comments given by seven peer‐reviewers on the initial manuscript. The reviewers’ comments have helped the author tremendously in improving the book.

      I