Topics in Current Chemistry

Transcription

1 289 Topics in Current Chemistry Editorial Board: V. Balzani A. de Meijere K.N. Houk H. Kessler J.-M. Lehn S. V. Ley M. Olivucci S. Schreiber J. Thiem B. M. Trost P. Vogel F. Vögtle H. Wong H. Yamamoto

2 Topics in Current Chemistry Recently Published and Forthcoming Volumes Orbitals in Chemistry Volume Editor: Vol. 289, 2009 Glycoscience and Microbial Adhesion Volume Editors: Thisbe K. Lindhorst, Stefan Oscarson Vol. 288, 2009 Templates in Chemistry III Volume Editors: Broekmann, P., Dötz, K.-H., Schalley, C.A. Vol. 287, 2009 Tubulin-Binding Agents: Synthetic, Structural and Mechanistic Insights Volume Editor: Carlomagno, T. Vol. 286, 2009 STM and AFM Studies on (Bio)molecular Systems: Unravelling the Nanoworld Volume Editor: Samorì, P. Vol. 285, 2008 Amplification of Chirality Volume Editor: Soai, K. Vol. 284, 2008 Anthracycline Chemistry and Biology II Mode of Action, Clinical Aspects and New Drugs Volume Editor: Krohn, K. Vol. 283, 2008 Anthracycline Chemistry and Biology I Biological Occurence and Biosynthesis, Synthesis and Chemistry Volume Editor: Krohn, K. Vol. 282, 2008 Photochemistry and Photophysics of Coordination Compounds II Volume Editors: Balzani, V., Campagna, S. Vol. 281, 2007 Photochemistry and Photophysics of Coordination Compounds I Volume Editors: Balzani, V., Campagna, S. Vol. 280, 2007 Metal Catalyzed Reductive C C Bond Formation A Departure from Preformed Organometallic Reagents Volume Editor: Krische, M. J. Vol. 279, 2007 Combinatorial Chemistry on Solid Supports Volume Editor: Bräse, S. Vol. 278, 2007 Creative Chemical Sensor Systems Volume Editor: Schrader, T. Vol. 277, 2007 In situ NMR Methods in Catalysis Volume Editors: Bargon, J., Kuhn, L. T. Vol. 276, 2007 Sulfur-Mediated Rearrangements II Volume Editor: Schaumann, E. Vol. 275, 2007 Sulfur-Mediated Rearrangements I Volume Editor: Schaumann, E. Vol. 274, 2007 Bioactive Conformation II Volume Editor: Peters, T. Vol. 273, 2007 Bioactive Conformation I Volume Editor: Peters, T. Vol. 272, 2007

3 Orbitals in Chemistry Volume Editor: With Contributions by S. Inagaki M. Ishida J. Ma Y. Naruse T. Ohwada Y. Wang

4 Editor Gifu University Faculty of Engineering Department of Chemistry 1-1 Yanagido Gifu Japan ISSN e-issn ISBN e-isbn DOI / Springer Heidelberg Dordrecht London New York Library of Congress Control Number: Springer-Verlag Berlin Heidelberg 2009 This work is subject to copyright. All rights are reserved, whether the whole or part of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, roadcasting, reproduction on microfilm or in any other way, and storage in data banks. Duplication of this publication or parts thereof is permitted only under the provisions of the German Copyright Law of September 9, 1965, in its current version, and permission for use must always be obtained from Springer. Violations are liable to prosecution under the German Copyright Law. The use of general descriptive names, registered names, trademarks, etc. in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use. Cover design: WMXDesign GmbH, Heidelberg, Germany Printed on acid-free paper Springer is part of Springer Science+Business Media (

5 Volume Editor Gifu University Faculty of Engineering Department of Chemistry 1-1 Yanagido Gifu Japan Editorial Board Prof. Dr. Vincenzo Balzani Dipartimento di Chimica G. Ciamician University of Bologna via Selmi Bologna, Italy vincenzo.balzani@unibo.it Prof. Dr. Armin de Meijere Institut für Organische Chemie der Georg-August-Universität Tammanstr Göttingen, Germany ameijer1@uni-goettingen.de Prof. Dr. Kendall N. Houk University of California Department of Chemistry and Biochemistry 405 Hilgard Avenue Los Angeles, CA , USA houk@chem.ucla.edu Prof. Dr. Horst Kessler Institut für Organische Chemie TU München Lichtenbergstraße Garching, Germany kessler@ch.tum.de Prof. Dr. Jean-Marie Lehn ISIS 8, allée Gaspard Monge BP Strasbourg Cedex, France lehn@isis.u-strasbg.fr Prof. Dr. Steven V. Ley University Chemical Laboratory Lensfield Road Cambridge CB2 1EW Great Britain Svl1000@cus.cam.ac.uk Prof. Dr. Massimo Olivucci Università di Siena Dipartimento di Chimica Via A De Gasperi Siena, Italy olivucci@unisi.it Prof. Dr. Stuart Schreiber Chemical Laboratories Harvard University 12 Oxford Street Cambridge, MA , USA sls@slsiris.harvard.edu

6 vi Prof. Dr. Joachim Thiem Institut für Organische Chemie Universität Hamburg Martin-Luther-King-Platz Hamburg, Germany thiem@chemie.uni-hamburg.de Prof. Dr. Barry M. Trost Department of Chemistry Stanford University Stanford, CA , USA bmtrost@leland.stanford.edu Prof. Dr. Pierre Vogel Laboratory of Glycochemistry and Asymmetric Synthesis EPFL Ecole polytechnique féderale de Lausanne EPFL SB ISIC LGSA BCH 5307 (Bat.BCH) 1015 Lausanne, Switzerland pierre.vogel@epfl.ch Prof. Dr. Henry Wong The Chinese University of Hong Kong University Science Centre Department of Chemistry Shatin, New Territories hncwong@cuhk.edu.hk Prof. Dr. Hisashi Yamamoto Editorial Board Arthur Holly Compton Distinguished Professor Department of Chemistry The University of Chicago 5735 South Ellis Avenue Chicago, IL USA yamamoto@uchicago.edu Prof. Dr. Fritz Vögtle Kekulé-Institut für Organische Chemie und Biochemie der Universität Bonn Gerhard-Domagk-Str Bonn, Germany voegtle@uni-bonn.de

7 Topics in Current Chemistry Also Available Electronically Topics in Current Chemistry is included in Springer s ebook package Chemistry and Materials Science. If a library does not opt for the whole package the book series may be bought on a subscription basis. Also, all back volumes are available electronically. For all customers who have a standing order to the print version of Topics in Current Chemistry, we offer the electronic version via SpringerLink free of charge. If you do not have access, you can still view the table of contents of each volume and the abstract of each article by going to the SpringerLink homepage, clicking on Chemistry and Materials Science, under Subject Collection, then Book Series, under Content Type and finally by selecting Topics in Current Chemistry. You will find information about the Editorial Board Aims and Scope Instructions for Authors Sample Contribution at springer.com using the search function by typing in Topics in Current Chemistry. Color figures are published in full color in the electronic version on SpringerLink. Aims and Scope The series Topics in Current Chemistry presents critical reviews of the present and future trends in modern chemical research. The scope includes all areas of chemical science, including the interfaces with related disciplines such as biology, medicine, and materials science. The objective of each thematic volume is to give the non-specialist reader, whether at the university or in industry, a comprehensive overview of an area where new insights of interest to a larger scientific audience are emerging. vii

8 viii Topics in Current Chemistry Also Available Electronically Thus each review within the volume critically surveys one aspect of that topic and places it within the context of the volume as a whole. The most significant developments of the last 5 10 years are presented, using selected examples to illustrate the principles discussed. A description of the laboratory procedures involved is often useful to the reader. The coverage is not exhaustive in data, but rather conceptual, concentrating on the methodological thinking that will allow the non-specialist reader to understand the information presented. Discussion of possible future research directions in the area is welcome. Review articles for the individual volumes are invited by the volume editors. In references Topics in Current Chemistry is abbreviated Top Curr Chem and is cited as a journal. Impact Factor 2008: 5.270; Section Chemistry, Multidisciplinary : Rank 14 of 125

9 Preface Molecular properties and reactions are controlled by electrons in the molecules. Electrons had been thought to be particles. Quantum mechanics showed that electrons have properties not only as particles but also as waves. A chemical theory is required to think about the wave properties of electrons in molecules. These properties are well represented by orbitals, which contain the amplitude and phase characteristics of waves. This volume is a result of our attempt to establish a theory of chemistry in terms of orbitals A Chemical Orbital Theory. The amplitude of orbitals represents a spatial extension of orbitals. An orbital strongly interacts with others at the position and in the direction of great extension. Orbital amplitude controls the reactivities and selectivities of chemical reactions. In the first paper on frontier orbital theory by Fukui the amplitude appeared in the form of its square, i.e., the density of frontier electrons in 1952 (Scheme 1). Orbital mixing rules were developed by Libit and Hoffmann and by Inagaki and Fukui in 1974 and Hirano and Imamura in 1975 to predict magnitudes of orbital amplitudes (Scheme 2) for understanding and designing stereoselective reactions. Scheme 1 From electron density to orbital amplitude ix

10 x Preface Scheme 2 Orbital mixing changes amplitudes The history of orbital phase can be traced back to the theory of chemical bond or bonding and antibonding orbitals by Lennard-Jones in The second milestone was the discovery of the importance of orbital symmetry in chemical reactions, pointed out by Fukui in 1964 (Scheme 3) and established by Woodward and Scheme 3 Orbital symmetry

11 Preface xi Hoffmann in Ten years later, Fukui and Inagaki proposed an orbital phase theory for cyclic molecules and transition states, which includes the Woodward- Hoffmann rule and the Hueckel rule for aromaticity (Scheme 4). In 1982 Inagaki Scheme 4 Orbital phase and Hirabayashi disclosed cyclic orbital interactions even in noncyclic conjugated systems (Scheme 5). The orbital phase was shown to control noncyclic as well as cyclic systems. The orbital phase theory has since expanded and is still expanding the scope of its applications. Scheme 5 Cyclic orbital interaction in noncyclic conjugation

12 xii Preface One day Fukui sent me an article where Dirac wrote [Dirac PAM (1972) Fields and Quanta, 3:139]:... However, the one fundamental idea which was introduced by Heisenberg and Schroedinger was that one must work with noncommutative algebra.... The question arises whether the noncommutation is really the main new idea of quantum mechanics. Previously I always thought it was but recently I have begun to doubt it.... So the real genius of Heisenberg and Schroedinger, you might say, was to discover the existence of probability amplitudes containing this phase quantity which is very well hidden in nature. Dirac thought that amplitude and phase are keywords in quantum mechanics. His words encouraged me in the early days, although he was not referring to amplitude and phase of orbitals. In the first chapter, a theory for the interactions of two orbitals is briefly summarized for students or chemists who are not familiar with orbitals and for readers to understand the theoretical background common to all the other chapters of this volume. In the second chapter, the mechanism of chemical reactions is proposed to form a spectrum composed of a delocalization band a pseudoexcitation band a transfer band. In the third chapter, a theory for the interactions of three orbitals is described and applications of orbital mixing rules to stereoselective organic reactions are reviewed. In the fourth chapter, an orbital phase theory for cyclic orbital interactions and its applications are described and reviewed. In the fifth chapter, orbital phase in the environments of reaction centers is shown to control stereoselectivities of organic reactions. In the sixth chapter, p-facial selectivities of Diels- Alder reactions are reviewed. In the seventh chapter, the orbital phase theory is applied to designing persistent singlet localized diradicals. In the eighth chapter, a theory for the relaxation of small ring strains is described and reviewed and in the ninth chapter, the chemical orbital theory is shown to be helpful in thinking about inorganic molecules as well. The chemical orbital theory has been established almost as described in this volume. The theory is useful and reliable for thinking about molecules and reactions. In the future, applications will shift more and more from understanding to designing molecules and reactions. I appreciate the help and encouragement offered to me by Prof. Hisashi Yamamoto of the University of Chicago. Summer 2009

13 Contents Elements of a Chemical Orbital Theory... 1 A Mechanistic Spectrum of Chemical Reactions Orbital Mixing Rules An Orbital Phase Theory Orbital Phase Environments and Stereoselectivities Tomohiko Ohwada p-facial Selectivity of Diels-Alder Reactions Masaru Ishida and Orbital Phase Design of Diradicals Jing Ma,, and Yong Wang Relaxation of Ring Strains Yuji Naruse and Orbitals in Inorganic Chemistry: Metal Rings and Clusters, Hydronitrogens, and Heterocyles Index xiii