It seems likely that no project of this magnitude is undertaken in the absence of several motivations. This book is no exception. There are, from our perspective, at least two rational reasons for conducting this cataloging and organizational effort. The first of these is the obvious fact that a very large number of macrocyclic polyethers have now been prepared and nowhere is there a comprehensive listing of them. A number of excellent reviews have been published dealing with one or more aspects of macrocycle chemistry, but we felt a great need for a single source listing known compounds. We have, the- fore, attempted to provide such a listing to assist ourselves in keeping track as well as, we hope, helping others in this field. We also felt that there was a need for a survey of methods which have been utilized in the syntheses of these cation binders so that the novice could establish some starting point. Wherever possible, we have also attempted to point to the motivations which en gendered the various syntheses. The somewhat irrational reason which propelled us into this endeavor was the ques tioning of Charlie Morgan who often asked if one or another obscure compound had been synthesized. As often as not, we were uncertain arid now at least have a reference which, if not absolutely complete, will at least save face.

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Introduction and General Principles.- 1.1 Background.- 1.2 Pedersen's Discovery of Crown Compounds.- 1.3 Nomenclature and Jargon.- 1.3.1 Crown Ether.- 1.3.2 Azacrown.- 1.3.3 In-Out Bicyclic Amines.- 1.3.4 Cryptands and Cryptate Complexes.- 1.3.5 Lariat Ethers.- 1.3.6 Crown Esters.- 1.3.7 Spherands.- 1.3.8 Cascades.- 1.3.9 Polypodes and Octopus Molecules.- 1.3.10 Host-Guest-Chemistry.- 1.3.11 Conventions.- 1.4 The Cyclooligomerization of Ethylene Oxide.- 1.5 Polyazamacrocycles as Complexing Agents for Transition Metals.- 1.6 References.- 2. The Template Effect.- 2.1 Introduction.- 2.2 Operation of the Template Effect.- 2.3 Evidence for the Template Effect.- 2.4 Complexation Constants and the Template Effect.- 2.5 References.- 3. Syntheses of Oxygen Macrocycles.- 3.1 Pedersen's First Crowns.- 3.2 Syntheses of 18-Crown-6.- 3.3 Syntheses of Dibenzo and Dicyclohexano-18-Crown-6.- 3.4 Synthesis of Substituted Benzocrowns.- 3.5 Crowns Incorporating the Xylylene Unit.- 3.6 Furan-containing Macrocycles.- 3.7 Crowns Containing the Paracyclophanyl Unit.- 3.8 Bis-Crowns.- 3.9 Lariat Ethers.- 3.10 Miscellaneous Crown Systems.- 3.11 Ne wkome's Pyridine-containing Macrocycles.- 3.12 Okahara's One-pot Approach.- 3.13 Chiral Crowns.- 3.13.1 Cram's Chiral Binaphthyl Systems.- 3.13.2 Crowns Incorporating the Tartaric or Lactic Acid Subunit.- 3.13.3 Crowns Incorporating Sugar Subunits.- 3.14. Organometallic Derivatives of Crowns.- 3.15 Cesium Salts in Crown Synthesis.- 3.16 Listings of Tables.- 3.17 Tables 3.13.29.- 3.18 References.- 4. Syntheses of Azacrowns.- 4.1 Introduction.- 4.2 Monoazacrowns.- 4.3 Bridged Monoazacrowns.- 4.4 Diazacrowns.- 4.5 Cyclams.- 4.6 Cyclic Oximes.- 4.7 Macrocyclic Imines.- 4.8 Thioazamacrocycles.- 4.9 Biologically Active Azacrowns.- 4.10 CrownEther Based Dyes.- 4.11 Newkome's Pyridine-containing Macrocycles.- 4.12 Listing of Tables.- 4.13 Tables 4.14.21.- 4.14 References.- 5. Crown Esters and Macrocyclic Polyether Lactones.- 5.1 Introduction.- 5.2 General Ester Synthesis.- 5.3 Macrocyclic Ester Properties.- 5.4 One-pot Macrocyclic Lactone Synthesis.- 5.5 The Hantzsch Condensation.- 5.6 Antibiotic Models.- 5.7 Stannoxanes as Covalent Templates.- 5.8 Macrocyclic Esters by Ozonolysis.- 5.9 Photochemical Macrocyclization.- 5.10 Listing of Tables.- 5.11 Tables 5.15.14.- 5.12 References.- 6. Miscellaneous Macrocycles.- 6.1 Macrocyclic Polyether Acetals.- 6.2 Macrocyclic Thioethers.- 6.2.1 Simple Sulfur Macrocycles.- 6.2.2 Macrocycles with Sulfur-containing Subunits.- 6.2.3 Macrocyclic Polysulfides.- 6.3 Mixed Sulfur-Nitrogen Macrocycles.- 6.4 Phosphorus and Arsenic-containing Macrocycles.- 6.5 Silicon-containing Macrocycles.- 6.6 Polymer-bound Macrocycles.- 6.6.1 Pendant Crown Polymers.- 6.6.2 Crown Ether Copolymers.- 6.6.3 Polycrowns.- 6.6.4 Pseudocrowns.- 6.7 Listing of Tables.- 6.8 Tables 6.16.4.- 6.9 References.- 7. Open-chained Equivalents of Crown Ethers.- 7.1 Introduction.- 7.2 Uses of Open-chained Equivalents in PTC.- 7.3 Octopus Molecules.- 7.4 Substituted Podands.- 7.5 Synthetic Ionophores.- 7.6 Listing of Tables.- 7.7 Tables 7.17.13.- 7.8 References.- 8. Cryptands and Related Poly cyclic Systems.- 8.1 Inception and General Syntheses.- 8.2 Cryptands Containing Sulfur and Nitrogen in the Bridges.- 8.3 Lipophilic Cryptands.- 8.4 Cryptands Containing a Carbon Bridgehead.- 8.5 Chiral Cryptands.- 8.6 Miscellaneous Cryptands.- 8.7 Macropolycyclic Cryptands.- 8.8 Polymer-bound Cryptands.- 8.9 listing of Tables.- 8.10 Tables 8.18.5.- 8.11 References.- Author Index.