Hydrogen-bonded capsules: molecular behavior in small spaces

228 Pages·2016·15.486 MB·English

by  Rebek, Julius

Hydrogen-bonded Capsules
Molecular Behavior in Small Spaces
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Hydrogen-bonded Capsules
Molecular Behavior in Small Spaces
Julius Rebek, Jr.
Fudan University, China & The Scripps Research Institute, USA
World Scientific
NEW JERSEY • LONDON • SINGAPORE • BEIJING • SHANGHAI • HONG KONG • TAIPEI • CHENNAI • TOKYO
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Published by
World Scientific Publishing Co. Pte. Ltd.
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Library of Congress Cataloging-in-Publication Data
Rebek, Julius, Jr.
Hydrogen-bonded capsules : molecular behavior in small spaces / Julius Rebek, Jr.,
Fudan University, China & The Scripps Research Institute, USA.
pages cm
Includes bibliographical references and index.
ISBN 978-9814678353 (hardcover : alk. paper) -- ISBN 981467835X (hardcover : alk. paper)
1. Nanochemistry. 2. Microencapsulation. 3. Hydrogen bonding. 4. Chemistry, Organic. I. Title.
QC176.8.N35R42 2015
541'.2--dc23
2015023647
British Library Cataloguing-in-Publication Data
A catalogue record for this book is available from the British Library.
Copyright © 2016 by World Scientific Publishing Co. Pte. Ltd.
All rights reserved. This book, or parts thereof, may not be reproduced in any form or by any means,
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Printed in Singapore
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For
Stephen L. Buchwald and Jin-Quan Yu
Architects of chemical catalysis
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Contents
Prologue 1
Chapter 1 Spherical and Similar Capsules 3
Chapter 2 Calixarene Capsules 37
Chapter 3 The Cylindrical Capsule 57
Chapter 4 Hexameric Capsules from Resorcinarenes
and Pyrogallolarenes 99
Chapter 5 Stereochemistry of Confined Molecules 117
Chapter 6 Chiral Capsules 133
Chapter 7 Expanded and Contracted Capsules 153
Chapter 8 Reactions Inside Capsules 191
Index 219
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Prologue
Research on molecular recognition became a fashionable topic for
physical organic chemists in the 1980s. At the time there was grow-
ingdisenchantmentwiththenonclassicalioncontroversy,andorbital
symmetry fatigue was taking hold in the community. But the discov-
ery of crown ethers by Pedersen in 1962 ignited the study of their
complexeswithions,andmacrocyclicpolyethersdominatedthescene
fordecades.Theweakintermolecularinteractionsofthesecomplexes
gave rise to the concepts of molecular recognition: complementarity
ofsizes,shapesandchemicalsurfaces.Theculminationofthisactivity
wastheawardoftheNobelPrizeinChemistrytoPedersen,Cramand
Lehnin1987forestablishinghost–guestchemistryand,onagrander
scale, supramolecular chemistry.
Whilemostpractitionersfavoredmacrocycliccompoundsforthe
recognitionofions,therewereseveralgroupswhopursuedreceptors
of different shapes for other molecular targets. The shapes included
a number of concave surfaces and — in our case — clefts, optimized
for the study of reversible interactions. Along with many others, we
became proficient in sculpting molecular surfaces to complement the
convex surfaces of the small molecular targets. This activity was a
departurefromtargetingsphericalionswithcircularreceptors—the
low-hangingfruit—sinceneutralmoleculetargetscomeinallmanner
ofsizesandshapes.Theapplicationofhydrogenbondingforrecogni-
tion purposes offered much appeal and became suspiciously close to
thebase-pairingofDNA.Purines,pyrimidinesandotherheterocyclic
bases,richinhydrogen-bondingpossibilities,becamepopulartargets.
We pursued synthetic receptors that contacted incresingly large frac-
tions of surfaces of the target molecules, and it became a reasonable
1