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253 Pages·1988·15.427 MB·English
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49 Topics in Current Chemistry Molecular Inclusion and Molecular Recognition- setarhtalC II Editor: E.Weber With Contributions by R. Bishop, M. Czugler, .I G. Dance, I. Goldberg, .J Rebek, Jr., .F Toda, E.Weber With 031 Figures and 54 Tables Springer-Verlag Berlin Heidelberg NewYork London Paris Tokyo This series presents critical reviews of the present position and future trends in modern chemical research. It is addressed to all research and industrial chemists who wish to keep abreast of advances in their subject. As a rule, contributions are specially commissioned.T he editors and publishers will, however, always be pleased to receive suggestions and supplementary information. Papers are accepted for "Topics in Current Chemistry" in English. ISBN 3-83391-045-3 Springer-Verlag Heidelberg Berlin New York ISBN 3-83391-783-0 Springer-Verlag New York Heidelberg Berlin Library of Congress Cataloging-in-Publication Data Molecular and inclusion molecular recognition -- clathrates II. current in (Topics chemistry ; )941 index. Includes .1 Clathratecompounds. I. Weber, .E I[. Bishop, R. [I[. Series. QD1.F58 vq].149 [QD474] 540s 59951-88 ISBN 3-83391-783-0 (U.S.) ]2'2.145[ subject This work is to copyright. llA the whole whether are rights reserved, or part of the material is concerned, yllacificeps the righis of translation, reprinting, re-use of illustra- tions, recitation, broadcasting, reproduction on microfilms or in other ways, ,ra d storage in data banks. Duplication of this publication or'parts thereof is only det:limrep under the provisions of the German Copyright Law of September ,9 ,5691 in sti version of June ,42 ,5891 and a co#yright eef must always be paid. Violations fall under the prose- cution act of the German Copyright Law. © Heidelberg Berlin Springer-Verlag 8891 Printed in GDR The use of registered names, trademarks, etc. in this publication does not imply, even in the absence of a statement, specific that such names are exempt from the relevant protective and laws regulations and therefore free for use. general Bookbinding: L/ideritz & Bauer, Berlin 012345-0203/1512 Guest Editor Professor Dr. Edwin Weber Institut f~r Organische Chemie und Biochemie der Universit/it Bonn, Gerhard-Domagk-Str. ,1 D-5300 Bonn 1 Editorial Board Prof. Dr. Michael J. S. Dewar Department of Chemistry, The University of Texas Austin, TX ,21787 USA Prof. Dr. Jack D. Dunitz Laboratorium rQf der Chemic Organische Hochschule Eidgen6ssischen eBartsst~tisrevinU Z/irich CH-8006 6/8, Prof. Dr. Klaus Hafner Institut f~ der Chemie Organische TH eBartsnesreteP ,51 Darmstadt D-6100 Prof. Dr. Edgar Heilbronner Institut der Universit/it Physikalisch-Chemisches eBartsgreblegnilK ,08 CH-4000 lesaB Prof. Dr. ,~h6/t6 Department of Chemistry, Tohoku University, Scndai, Japan 089 Prof. Dr. Jean-Marie Lehn de Institut Strasbourg, de Chimie, Universit6 ,1 rue esialB Pascal, .B .P Z 296/R8, 80076-F Strasbourg-Cedex Prof. Dr. Kurt Niedenzu University of Kentucky, College of Arts and secneicS Department of Chemistry, Lexington, KY ,60504 USA Prof. Dr. Kenneth N. Raymond Department of Chemistry, University of California, ,yelekreB California ,02749 USA Prof. Dr. Charles W. Rees Hofmann Professor of Department Organic Chemistry, of College Imperial Chemistry, of ecneicS Technology, and South Kensington, London 7WS 2AY, England Prof. Dr. Fritz Viigtle Institut Organische Chemie fiir und eimehcoiB Gerhard-Domagk-Str. der Universifftt, ,1 0035-D Bonn 1 Table of Contents Preface . . . . . . . . . . . . . . . . . . . . . . . IX The Significance of Molecular Type, Shape and Complementarity in Clathrate Inclusion I. Goldherg . . . . . . . . . . . . . . . . . . . . . Functional Group Assisted Clathrate Formation -- Scissor-Like and Roof-Shaped Host Molecules E. Weber, M. Czugler . . . . . . . . . . . . . . . . . 45 New Types of Helical Canal Inclusion Networks R. Bishop, I. G. Dance . . . . . . . . . . . . . . . . 137 Recent Progress in Molecular Recognition J. Rebek, Jr . . . . . . . . . . . . . . . . . . . . . . 189 Reaction Control of Guest in Compounds Host-Guest Inclusion Complexes F. Toda . . . . . . . . . . . . . . . . . . . . . . . 211 Index Author Volumes 101-149 . . . . . . . . . . . . . 239 Table of Contents of Volume 041 Molecular Inclusion and Molecular Recognition -- Clathrates I Preface Clathrate Chemistry Today -- Some Problems and Reflections E. Weber Separation of Enantiomers by Ciathrate Formation D. Worsch, F. V6gtle Isolation and Optical Resolution of Materials Utilizing Inclusion Crystallization F. Toda Tri-o-Thymotide Clathrates R. Gerdil Structural Parsimony and Structural Variety Among Inclusion Complexes F. H. Herbstein Inclusion Properties of Tetraphenylene and Synthesis of Its Derivatives T. C. W. Mak, H. N. C. Wong Preface This book is the second of a two-volume series that attempts to bring together in-depth investigations in currently important areas of "'molecular inclusion and molecular recognition" mainly based on clathrate formation. The first volume of this series (Volume 140) was published in 1987. The well-known fact that certain biological compounds (enzymes, carriers, etc.) can bind substrates selectively while markedly enhancing their chemical modifica- tion or transporting them through membranes has inspired chemists to design and synthesize molecules capable of mimicking these and other features. Remarkable progress has already been achieved in the preparation of macrocycles and related systems which combine specifically with ions as well as with various uncharged mole- cules and provide functional properties based on recognition, binding, catalysis, and transport of ions and molecules. The 1987 Nobel Prize for chemistry was awarded to the trio of scientists Pedersen, Cram, and Lehn who did fundamental work on this relatively new field, called "'host-guest" or "supramolecular chemistry" [cf. Weber, E., Vrgtle, F.: Nachr. Chem. Tech. Lab. 35, 1149 (1987)]. A supramolecular species (host-guest compound) results from the interaction of a. substrate (the guest) with its receptor molecule (the host). Normally one fienndcsl osure of the guest molecule in the cavity formed by a host framework (cf. crown complexes, cryptates). The host-guest association is not established by covalent and ionic bonds, but is caused by H-bonds and/or van der Waals interactions. With reference to the chemistry of weak intermolecular bonds, supramolecular association has contributed to the fundamental understanding of the elementary interactions on which molecular recognition and binding is based and represents an interface between chemistry and biology. Within this approach, clathrates (for a definition see Chapter 1 in Vol. 041 of this series) and related lattice-type aggregates may be considered as ralucelomarpus-itlum systems where guest molecules are included in a crystal matrix. They allow a great many applications which have been specified in Vol. 140, first of all the separation of enantiomersb y enantioselective recognition and inclusion of racemic guest molecules. Unfortunately, chemistry of clathrates has not made such rapid progress as the organic complexes until recently. Now new approaches and techniques have amply encouraged the design of selective host molecules and clathrate structures. The aim of this book is to illustrate important developments in these fields including functional group assisted clathrates, helical channel formation, architecture of crystalline clefts, and other molecular design principles given in Chapters 1-4, while Chapter 5 is devoted to the fascinating possibilities of stereocontrolled solid-state reactions using clathrate inclusion. Thus the present book is not a mere sequel of Volume 140 (part I of this topic) published in 1987, but complements the theme. Both books could only be completed with the assistance of the individual contributing authors. Their efforts cannot be underestimated, and the editor wishes to express his heartfelt appreciation. Bonn, April 1988 Edwin Weber The Significance of Molecular Type, Shape dna Complementarity in Clathrate Inclusion Israel Goidberg School of Chemistry, Sackler Faculty of 69978 University, Ramat-Aviv, Tel-Aviv Exact Sciences, Israel Table of Contents 1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 2 Solvates and Clathrates as Common Phenomena . . . . . . . . . . . . . 3 2.1 General Considerations . . . . . . . . . . . . . . . . . . . . . . 3 2.2 Solvates -- The Simplest Example of Lattice Inclusion . . . . . . . . 3 2.3 Channels and Cages in Organic Lattices . . . . . . . . . . . . . . . 12 3 Molecular Design of Hosts for the Formation of Inclusion Compounds with Apolar Guests . . . . . . . . . . . . . . . . . . . . . . . . . . . 18 3.1 Background -- Clathrate Inclusion Compounds of Spirotriphosphazenes 81 3.2 "Wheel-and-Axle" Type of Host Molecules in Clathrate Inclusion . 91 3.3 Substituted Allenes as Clathrate Hosts . . . . . . . . . . . . . . . 22 4 Selective Complexations of Polar Guests by Hosts Containing Functional "Sensors" . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24 4.1 Coordinato-Clathrates of N,N'-Ditritylurea . . . . . . . . . . . . . 25 4.2 Separation of Structural Isomers by Crystalline Complexation with 1,1- Di(p-hydroxyphenyl)cyclohexane . . . . . . . . . . . . . . . . . 30 4.3 Chiral Inclusion Complexes of 2,2'-Dihydroxy-l,l'-Binaphthyl with Phosphinates and Phosphine Oxides . . . . . . . . . . . . . . . . 38 5 Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . 43 6 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43 scipoT in Current Chemistry, Vol. 941 © Springer-Vetlag, Berlin Heidelberg 8891 learsI grebdloG 1 Introduction The formation of clathrate inclusion compounds in which guest species are enclosed by channels or cages that occur in a given host lattice was first discovered in the middle of the past century ,~1 Since then a large number of clathrates and solvates, found mostly by chance as by-products of research in other areas, have been charac- terized 2-4~. These multicomponent systems attracted however relatively little atten- tion, and a systematic development of their chemistry was very slow. The rapid advancement of host-guest chemistry in the last two decades, since the pioneering work of Pedersen on crown ethers ,)5 provided a turning point in this respect. Initially, the class of molecular inclusion complexes, in which larger host species are able to enclose and bind smaller guest molecules, has been subjected to most intensive investi- gations aiming at the synthesis of molecular models that can mimic the chemical behaviour of natural systems. The success was overwhelming with respect to the number and complexity of suitable compounds (ligand-substrate complexes, iono- phores, molecular receptors) that have been prepared and analyzed. Most extensively studied were macro(poly)cyclic hosts of the crown/cryptate type which turned out to be excellent and often selective complexors of metal ions and amino acid deri- vatives 6-s). The presence of O and/or N heteroatoms in these macrocycles made them also suitable for an effective complexation through hydrogen bonding with uncharged guest molecules containing proton donating sites such as acidic CH, NH or OH 9-11k Most recent investigations of models for molecular separation and transport processes relate to carefully designed organic systems which involve encapsulation of apolar guests within apolar host molecules )4~-z1 As a natural development of the successful molecular inclusion concept, which involved electrostatic 6-u~ as well as van der Waals x2-14) forces between the inter- acting host and guest entities, an increasing interest has been shown in the systematic study of lattice-inclusion type systems. A considerable effort has been devoted to the design of new hosts for the formation of stable crystalline clathrates and the improvement of selective complexations with potential guests. Suitable examples of clathrates studied in recent years include hosts such as Dianin's compounds ,)as~ perhydrotriphenylene ,)b51 cyclotriveratrylene ,)c51 triphenylmethane ,)d51 hexakis- (arylthio) and -(arylthiomethyl)benzenes ,)e51 tri-o-thymotide (TOT) ,)f51 and choleic acids )gs~ (cf. Fig. 1 in Ch. 1 of Vol. 140). Selected series of such clathrate inclusion systems have particularly been useful in research of photochemical reactions in the solid state ,6~ )7~ and of selective molecular complexation that is central to biological phenomena is, )9~ This report surveys the structural aspects ofclathrates formed with a series of other host systems, illustrating the conceptual progress made over the last few years in our ability to achieve a better controlled and more selective lattice-type complexa- tion of uncharged molecules. It also emphasizes an important observation that in molecular separations the approach of lattice inclusion can often be as effective and easy to apply as that of molecular inclusion; both phenomena utilize a similar variety of binding forces by which host and guest constituents are held together in a structured way. Most of the examples presented below were structurally analyzed in this laboratory, and they refer to systems based on organic host lattices only. They reflect on the author's general interest in structural aspects of host-gnest chemistry.

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