Classical Methods in Structure Elucidation of Natural Products
The structures of many natural products are given in standard textbooks on organic chemistry as 'established facts'. Yet for those natural products whose structures were determined between 1860 and 1960 by classical chemical methods, the lines of evidence are frequently buried under any number of investigations that led to dead ends and to revised structure assignments. Since very little is known about the structure clarification of these products at present, this volume serves to shed light once again on the achievements of previous generations of chemists, who worked with minimal experimental tools. The selection of the 25 representative examples is subjective and arbitrary, dictated by the author's pleasure in recovering fundamental milestones in organic chemistry, with each chapter devoted to one organic compound. The time period covered, however, is more precisely defined: 1860 represents the advent of structure theory, prior to which there was no conceptual framework to address the 'structure' of a compound. One hundred years later, 1960 approximately marks the change from classical structure elucidation to the era in which structure elucidation is mainly based on spectroscopic evidence and X-ray crystallography. Since the emphasis of this work is on classical structure elucidation, work performed later than 1960 is only considered in exceptional cases. Rather than simply provide a history of structure elucidation of particular natural products, the author combines results from historic experiments to trace a line of evidence for those structures that are nowadays accepted as established. This line of evidence may follow the path put forward by the original contributors, yet in some cases the experimental facts have been combined to form another, hopefully shorter, line of evidence. As a result, readers are able to ascertain for themselves the 'facts behind the established structure assignments' of a number of important natural products.
COMPOUNDS WITH ONLY OXYGEN FUNCTIONALITIES Ascorbic Acid Hinokitiol Ascorbic Acid Hinokitiol Cantharidine Camphor Alpha--Terpineol Lactaroviolin Santonine Estrone Alpha--Tocopherol COMPOUNDS WITH NITROGEN AND OXYGEN FUNCTIONALITIES Pyridoxine Muscarine Lupinine Lysergic Acid Riboflavine Cocaine Quinine Colchicine Luciferin Strychnine COMPOUNDS WITH ADDITIONAL FUNCTIONALITIES Biotin Thiamine Griseofulvin COMPOUNDS WITHOUT HETEROATOM-FUNCTIONALITIES Decacyclene Carotene CAN YOU DO IT YOURSELF? Penicillin
Reinhard W. Hoffmann is Professor Emeriti of the University of Marburg. He studied chemistry at the Universitat Bonn and received his Dr. rer. nat. in 1958 under the direction of Prof. B. Helferich. He spent two years as postdoctoral fellow at The Pennsylvania State University with Prof. G. W. Brindley and moved then to the Universitat Heidelberg for another postdoctoral year with Prof. G. Wittig. In 1964 he obtained his habilitation and in 1967 he moved as lecturer to the Technische Hochschule Darmstadt and in 1970 to his present position as Professor of Organic Chemistry at the Universitat Marburg. His research interests are new methods in stereoselective C-C-bond formation, their application in natural products synthesis and the stereochemistry of reactive organometallic compounds. More recent research activities concern combinatorial approaches to new catalysts and conformation design.
Organic chemistry as we know it today originated from a preoccupation with substances isolated from nature. In the period from 1860 to 1960, the main task was to elucidate their molecular structure by way of degradation and synthesis. In light of the limited experimental methods available and the lack of established reference compounds, this represented an unparalleled intellectual challenge. This book makes use of twenty-five representative examples to retrace the great accomplishments made by the generation of chemists during this era. At the same time, it questions the reliability of the experimental results when judged by today's criteria, particularly since the structures for numerous natural products are stated as established facts in standard text books. With each chapter devoted to one organic compound, the author combines results from historic experiments to trace a line of evidence that may follow the path put forward by the original contributors. However, in some cases the experimental facts have been combined to form another, hopefully shorter, line of evidence. As a result, readers are able to determine for themselves the 'facts behind the established structure assignments' of a number of important natural products.