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Modern Physical Organic Chemistry

Eric V. Anslyn The University of Texas, Austin
Dennis A. Dougherty California Institute of Technology


The twentieth century saw the birth of physical organic chemistry—the study of the interrelationships between structure and reactivity in organic molecules—and the discipline matured to a brilliant and vibrant field. Some would argue that the last century also saw the near death of the field. Undeniably, physical organic chemistry has had some difficult times. There is a perception by some that chemists thoroughly understand organic reactivity and that there are no important problems left. This view ignores the fact that while the rigorous treatment of structure and reactivity in organic structures that is the field’s hallmark continues, physical organic chemistry has expanded to encompass other disciplines.

In our opinion, physical organic chemistry is alive and well in the early twenty-first century. New life has been breathed into the field because it has embraced newer chemical disciplines, such as bioorganic, organometallic, materials, and supramolecular chemistries. Bioorganic chemistry is, to a considerable extent, physical organic chemistry on proteins, nucleic acids, oligosaccharides, and other biomolecules. Organometallic chemistry traces its intellectual roots directly to physical organic chemistry, and the tools and conceptual framework of physical organic chemistry continue to permeate the field. Similarly, studies of polymers and other materials challenge chemists with problems that benefit directly from the techniques of physical organic chemistry. Finally, advances in supramolecular chemistry result from a deeper understanding of the physical organic chemistry of intermolecular interactions. These newer disciplines have given physical organic chemists fertile ground in which to study the interrelationships of structure and reactivity. Yet, even while these new fields have been developing, remarkable advances in our understanding of basic organic chemical reactivity have continued to appear, exploiting classical physical organic tools and developing newer experimental and computational techniques. These new techniques have allowed the investigation of reaction mechanisms with amazing time resolution, the direct characterization of classically elusive molecules such as cyclobutadiene, and highly detailed and accurate computational evaluation of problems in reactivity. Importantly, the techniques of physical organic chemistry and the intellectual approach to problems embodied by the discipline remain as relevant as ever to organic chemistry. Therefore, a course in physical organic chemistry will be essential for students for the foreseeable future.

This book is meant to capture the state of the art of physical organic chemistry in the early twenty-first century, and, within the best of our ability, to present material that will remain relevant as the field evolves in the future. For some time it has been true that if a student opens a physical organic chemistry textbook to a random page, the odds are good that he or she will see very interesting chemistry, but chemistry that does not represent an area of significant current research activity. We seek to rectify that situation with this text. A student must know the fundamentals, such as the essence of structure and bonding in organic molecules, the nature of the basic reactive intermediates, and organic reaction mechanisms. However, students should also have an appreciation of the current issues and challenges in the field, so that when they inspect the modern literature they will have the necessary background to read and understand current research efforts. Therefore, while treating the fundamentals, we have wherever possible chosen examples and highlights from modern research areas. Further, we have incorporated chapters focused upon several of the modern disciplines that benefit from a physical organic approach. From our perspective, a protein, electrically conductive polymer, or organometallic complex should be as relevant to a course in physical organic chemistry as are small rings, annulenes, or nonclassical ions.

We recognize that this is a delicate balancing act. A course in physical organic chemistry cannot also be a course in bioorganic or materials chemistry. However, a physical organic chemistry class should not be a history course, either. We envision this text as appropriate for many different kinds of courses, depending on which topics the instructor chooses to emphasize. In addition, we hope the book will be the first source a researcher approaches when confronted with a new term or concept in the primary literature, and that the text will provide a valuable introduction to the topic. Ultimately, we hope to have produced a text that will provide the fundamental principles and techniques of physical organic chemistry, while also instilling a sense of excitement about the varied research areas impacted by this brilliant and vibrant field.

Eric V. Anslyn
Norman Hackerman Professor
University Distinguished Teaching Professor
University of Texas, Austin

 Dennis A. Dougherty
George Grant Hoag Professor of Chemistry
California Institute of Technology