(Reactivity and Structure Concepts in Organic Chemistry 2) Kenichi Fukui (auth.) - Theory of Orientation and Stereoselection-Springer-Verlag Berlin Heidelberg (1975)

Reactivity and Structure Concepts in Organic Chemistry Volume Editors: Klaus Hafner Charles W Rees Barry M Trost Jean-Marie Lehn P von R Schleyer Rudolf Zahradnik Kenichi Fukui Theory of Orientation and Stereoselection With 72 Figures Springer-Verlag Berlin Heidelberg New York 1975 Kenichi Fukui Kyoto University, Dept of Hydrocarbon Chemistry, Kyoto, Japan ISBN 978-3-642-61919-9 ISBN 978-3-642-61917-5 (eBook) DOI 10.1007/978-3-642-61917-5 Parts of this book have been published in Topics in Current Chemistry, Vol 15 (1970) Library of Congress Cataloging in Publication Data Fukui, Kenichi, 1918- Theory of orientation and stereoselection (Reactivity and structure; v 2) Bibliography: p Includes index Chemical reaction, Conditions and laws of Stereochemistry Chemistry, Physical organic I Title II Series QD501.F92 547'.1'223 75-25597 This work is subject to copyright All rights are reserved, whether the whole or part of the material is concerned, specifically those of translation, reprinting, re-use of illustrations, broadcasting, reproduction by photocopying machine or similar means, and storage in data banks Under § 54 of the German Copyright Law where copies are made for other than private use, a fee is payable to the publisher, the amount of the fee to be determined by agreement with the publisher © by Springer-Verlag Berlin' Heidelberg 1975 Softcover reprint of the hardcover 1st edition 1975 Typesetting: Hans Meister KG, Kassel, binding: Konrad Triltsch, Wiirzburg Preface Many organic chemists will agree with me that the old "electronic theory" has for a long time been inadequate for the interpretation of various new findings in chemistry, particularly for those of reactivity Considering the outstanding progress which has been made during the past 20 years in the interpretation of these facts, aided by the molecular orbital theory, the time has finally come for a new book showing what is within and what is beyond the reach of quantum-chemical methods It was therefore highly suitable that Dr F L Boschke of the SpringerVerlag suggested to me to make a contribution to a volume in the series "Topics in Current Chemistry" in February 1969 The article was published as Vol 15, No in June 1970 This new book is an expanded version of the article written in 1970 In this present volume several of the most up-to-date findings which have been gained in organic chemistry since then have been added It is highly probable that a certain "theoretical" design in the experimentalists' mind may have been the reason for these developments, whether they themselves are aware of it or not Theory produces new experimental ideas and conversely, a host of experimental data add another vista to new theories Due to the mutual beneficial effect of theory and experiment this book will always retain its value, although the quantum-chemical approach to the theory of reactivity is, of course, still in the developmental stage I t is my sincere hope that graduates and young research chemists, in both the theoretical and experimental fields will find this book useful and thereby become acquainted with the quantum-chemical way of thinking in which the concept of the "orbital" of an electron serves as a good explanation within the chemical terminology I extend my special thanks to Dr F L Boschke and Springer-Verlag for the planning and production of this book KENICHI FUKUI Kyoto, Japan, May 1975 Contents Molecular Orbitals Chemical Reactivity Theory Interaction of Two Reacting Species Principles Governing the Reaction Pathway General Orientation Rule Reactivity Indices Various Examples 7.1 Qualitative Consideration of the HOMO-LUMO Interaction 7.2 The Role of SOMO's 7.3 Aromatic Substitutions and Additions 7.4 Reactivity of Hydrogens in Saturated Compounds 7.5 Stereoselective Reactions 7.6 Subsidiary Effect 7.7 Rehybridization by Neighboring Group Effect Singlet-Triplet Selectivity Pseudoexcitation 10 Three-species Interaction 11 Orbital Catalysis 12 Thermolytic Generation of Excited States 13 Reaction Coordinate Formalism 14 Correlation Diagram Approach 15 The Nature of Chemical Reactions Appendix Principles Governing the Reaction Path An MO-Theoretical Interpretation Appendix II Orbital Interaction between Two Molecules References Author Index Subject Index 10 22 31 34 40 40 47 52 55 59 76 79 81 84 88 93 99 102 105 109 112 117 120 127 131 Molecular Orbitals Many chemical problems can be discussed by way of a knowledge of the electronic state of molecules The electronic state of a molecular system becomes known if we solve the electronic Schrodinger equation, which can be separated from the time-independent, nonrelativistic Schrodinger equation for the whole molecule by the use of the Born-Oppenheimer approximation 1) In this approximation, the electrons are considered to move in the field of momentarily fixed nuclei The nuclear configuration provides the parameters in the Schrodinger equation The nonrelativistic, electronic Schrodinger Hamiltonian operator, designated as H, is represented by H= !!;: (_ ~ L1t _ ~ za 8n m L ~ e2 ) ria 1-1 a + !!;: ~ + ~ ZaZ L ri} 1,}-1 (I