Modern Cyclophane Chemistry

by Gleiter, Rolf; Hopf, Henning

• ISBN13: 9783527307135
• ISBN10: 3527307133
• Edition: 1st
• Format: Hardcover
• Copyright: 2004-10-01
• Publisher: Wiley-VCH

Summary

Here, the editors Rolf Gleiter and Henning Hopf present an excellent overview of all the important aspects and latest results in cyclophane chemistry. Clearly structured and covering the entire range, the book introduces readers to the most recent research in the field. Twenty chapters, written by well-known scientists, cover in particular: synthesis of carbo- and heterocyclic cyclophanes and metallocenophanes structural and spectroscopic properties of cyclophanes current and future applications in synthesis and material science novel reactions of cyclophanes use of cyclophanes as building blocks in supramolecular chemistry for this fascinating class of compounds Thus, this is not only an extremely valuable source of information for synthetic organic chemists, but also a ready reference for scientists working in related fields of arene chemistry, stereoselective synthesis, material science, and bioorganic chemistry.

Author Biography

Born in 1940, Henning Hopf is Director of the Institute for Organic Chemistry at the TU Braunschweig. After studying chemistry in Goettingen and at the University of Wisconsin in Madison, where he gained his doctorate 1967, he qualified as a professor in 1972 at the University of Karlsruhe. Three years later he was offered a chair at the University of Wuerzburg and from there followed an offer of a professorship at Braunschweig in 1979. His<br> main areas of research concern hydrocarbon chemistry (alkines, allenes, cumulenes, aromats, cyclophanes, polyolefines, etc.) and mechanistic investigations of high-temperature reactions.<br> <br> <br> Rolf Gleiter is professor of chemistry at the UniversitSt Heidelberg. He studied chemistry and finished his doctoral thesis under the supervision of F. Effenberger in Stuttgart in 1964. From 1965 - 1968 he did postdoctoral work in the US, one year with P. v. R. Schleyer at Princeton and two years with R. Hoffmann at Cornell. He completed his habilitation with E. Heilbronner in Basel in 1972. In 1973 he moved as full professor to TU Darmstadt. In 1979 he took his present position. R. Gleiter is interested in intra- and intermolecular bonding properties by synthesizing model systems and investigation of their interactions by physical measurements supported by quantum chemical calculations.

Table of Contents

Preface	xv
List of Contributors	xvii
Cyclophynes	1	(40)
Yoshito Tobe
Motohiro Sonoda
Introduction	1	(1)
Orthocyclophynes and Related Systems	2	(15)
Planar Dehydrobenzoannulenes	3	(10)
Nonplanar Orthocyclophynes	13	(4)
Metacyclophynes and Related Systems	17	(11)
Paracyclophynes and 1,3,5-Bridged Cyclophynes	28	(7)
Concluding Remarks	35	(1)
Acknowledgement	36	(1)
References	36	(5)
Hetera (Cyclo-)phanes	41	(40)
Fritz Vogtle
Gregor Pawlitzki
Uwe Hahn
Introduction	41	(10)
Selection of Topics Presented	41	(1)
Definitions	42	(7)
Why Conduct a Survey on Heteraphanes?	49	(2)
Heteraphanes	51	(11)
Planar Chiral and Helical Chiral Phanes	51	(1)
Design of Phanes with Planar and Helical Chirality	51	(2)
Hetera [2.2]Metacyclophanes	53	(2)
Planar Chiral [2.2]Metacyclophanes	55	(1)
Planar Chiral Hetera [n]Para- and Hetera [n]Metacyclophanes	56	(1)
Dioxa [2.2]Phanes and Oxaza [2.2]Phanes	57	(1)
Enantiomer Separations	57	(1)
Strongly Helical Heteraphanes	58	(1)
Catenanes, Rotaxanes, and Knotanes of the Heteraphane Type	59	(1)
Template Synthesis of Rotaxanes Using Cyclophane Wheels	59	(1)
Higher Order [n]Rotaxanes via Non-ionic Template Effect	60	(1)
Combination of Anionic and Non-ionic Template	61	(1)
Molecular Knots and Similar Macrocycles of the Heteraphane Type	61	(1)
Further Heteraphanes, Metallaphanes and Supramolecular Phanes	62	(1)
Conclusions	62	(12)
Acknowledgement	74	(1)
References	74	(7)
Highly Strained Cyclophanes	81	(24)
Takashi Tsuji
Introduction	81	(1)
[n]Metacyclophanes	81	(8)
Synthesis	81	(2)
Structures and Physical Properties	83	(1)
Reactions of Strained [n]Metacyclophanes	84	(1)
Thermal and Photochemical Reactions	84	(1)
Addition Reactions	85	(1)
Reactions with Electrophiles	86	(1)
Reactions with Nucleophiles	87	(2)
[n]Paracyclophanes	89	(7)
Synthesis	90	(1)
Structures and Physical Properties	91	(1)
Reactions of Strained [n]Paracyclophanes	92	(1)
Thermal and Photochemical Reactions	92	(2)
Reactions with Electrophiles	94	(1)
Diels-Alder and Other Reactions	94	(1)
Kinetic Stabilization of [4]Paracyclophane Systems	95	(1)
Aromaticity of Bent Benzene Rings	96	(1)
Cyclophanes containing Polycyclic Aromatic Rings: (2,7)Pyrenophanes	96	(2)
[1,1]Paracyclophanes	98	(4)
Synthesis	99	(1)
Kinetic Stabilization of [1.1]Paracyclophane Systems	100	(1)
Structures and Physical Properties	100	(2)
References and Notes	102	(3)
Superphanes	105	(26)
Rolf Gleiter
Rolf Roers
Introduction	105	(1)
[n2]Cyclopropenonophanes	106	(3)
Synthesis	106	(3)
Superbridged Cyclopropenyliophanes	109	(1)
C4-Superphanes	109	(8)
Properties of Cyclobutadieno Superphanes	115	(1)
Oxidative Demetallations	116	(1)
C5-Superphanes	117	(3)
Superbridged Benzene Rings	120	(6)
Concluding Remarks	126	(1)
Acknowledgement	127	(1)
References	127	(4)
Carbon-Bridged Ferrocenophanes	131	(28)
Joon-Seo Park
T. Randall Lee
Introduction	131	(1)
Nomenclature	132	(1)
Mononuclear Carbon-Bridged Ferrocenophanes	133	(17)
[1]Ferrocenophanes	133	(1)
[2]Ferrocenophanes	134	(2)
[3]Ferrocenophanes	136	(4)
[4]Ferrocenophanes	140	(4)
[5]Ferrocenophanes	144	(2)
[m]Ferrocenophanes (m>5)	146	(1)
Multiply-Bridged Mononuclear Ferrocenophanes ([m]nFerrocenophanes)	147	(3)
Multinuclear Ferrocenophanes	150	(4)
[0.0]Ferrocenophanes	150	(1)
[1n]Ferrocenophanes	151	(2)
mn]Ferrocenophanes	153	(1)
Summary	154	(1)
References	154	(5)
Endohedral Metal Complexes of Cyclophanes	159	(30)
Rolf Gleiter
Bernhard J. Rausch
Rolf J. Schaller
Introduction	159	(1)
Singly-Bridged Group IVB Metallocenes	160	(3)
Singly-Carbon-Bridged Group IVB Metallocenes	160	(1)
Singly-Silicon-Bridged Group IVB Metallocenes	161	(1)
Singly-Boron- and Phosphorous-Bridged Group IVB Metallocenes	162	(1)
Doubly-Bridged Group IVB Metallocenes	163	(5)
Doubly-Carbon-Bridged Group IVB Metallocenes	163	(2)
Doubly-Silicon-Bridged Group IVB Metallocenes	165	(1)
Structural Features of Doubly-Bridged Group IVB Metallocenes	166	(2)
Endohedral Group VIB and VIIIB Metal π-Complexes	168	(8)
Bridged Bis[benzene]chromium Complexes	168	(2)
Bridged Metallocenophanes of Group VIIIB Metals	170	(6)
Cavities as Hosts for Cations of Group IB, IIIA and IVA Metals	176	(8)
Endohedral Silver Complexes with Cyclophanes	176	(4)
Silver Complexes with π-Prismands	180	(1)
Group IIIA and IVA Complexes of Cyclophanes	181	(1)
Group IIIA Complexes with π-Prismands	182	(2)
Concluding Remarks	184	(1)
Acknowledgments	184	(1)
References	184	(5)
Intramolecular Reactions in Cyclophanes	189	(22)
Henning Hopf
Introduction	189	(1)
Reactions between the Benzene Rings of Cyclophanes	190	(8)
The Pseudo-gem Effect	198	(3)
Intramolecular Reaction between Functional Groups in Cyclophanes	201	(6)
Conclusions	207	(1)
References	208	(3)
Reactive Intermediates from Cyclophanes	211	(18)
Wolfram Sander
Thermolysis of [2.2]Paracyclophanes	211	(6)
Photolytical Cleavage of [2.2]Paracyclophanes	217	(3)
Cleavage of [2.2]Paracyclophanes via Electron Transfer	220	(1)
Cleavage of Cyclophanes with Unsaturated Bridges	221	(2)
Cleavage of Cyclophanes with Carbonyl Groups in the Bridge	223	(3)
References	226	(3)
X-ray Crystal Structures of Porphyrinophanes as Model Compounds for Photoinduced Electron Transfer	229	(30)
Hermann Irngartinger
Thomas Oeser
Introduction	229	(1)
Porphyrin--Quinone Cyclophanes	230	(8)
Double-Bridged Porphyrin--Quinone Cyclophanes	230	(2)
Single-Bridged Porphyrin--Quinone Cyclophanes	232	(1)
Phenyl-Spacered Porphyrin--Quinone Cyclophanes	232	(3)
Naphthalene-Spacered Porphyrin-Quinone Cyclophanes	235	(3)
Porphyrin-Aromatic-Ring Cyclophanes	238	(15)
Single Bridge from Opposite meso-Positions	238	(1)
Substituted Phenyl Rings as Cyclophane Components	238	(5)
Polycyclic Aromatic Ring-Systems as Cyclophane Components	243	(2)
Aromatic Heterocycles as Cyclophane Components	245	(3)
Single Bridge from Opposite non-meso-Positions	248	(1)
Capped Porphyrins	249	(4)
Porphyrinophanes with Fullerene Hosts	253	(1)
Concluding Remarks	254	(1)
References	255	(4)
Ultraviolet Photoelectron Spectra of Cyclophanes	259	(16)
Heidi M. Muchall
Introduction	259	(4)
[2.2]Paracyclophane	263	(2)
Modified Bridges in [2.2]Paracyclophane	265	(1)
Conjugating Substituents in [2.2]Paracyclophane	266	(2)
Donor--Acceptor Cyclophanes	268	(2)
Heterocyclophanes	270	(1)
Miscellaneous Compounds	270	(3)
[6]Phanes with Higher Aromatic Systems	270	(1)
Cyclopropenophanes	271	(1)
Metacyclophanediynes	272	(1)
References	273	(2)
UV/Vis Spectra of Cyclophanes	275	(36)
Paul Rademacher
Introduction	275	(1)
Characteristic Properties of Cyclophanes with Implications for their Electronic Spectra	275	(2)
[n]Cyclophanes	277	(2)
[m.n]Paracyclophanes	279	(6)
[1.1]Paracyclophane	279	(1)
[2.2]Paracyclophane	280	(4)
[m.n]Paracyclophanes	284	(1)
Multibridged [2n]Cyclophanes and Related Compounds	285	(3)
[m.n]Arenophanes	288	(2)
[m.n]Naphthalenophanes	288	(1)
[n.n]Pyrenophanes	289	(1)
Fluorinated Cyclophanes	290	(1)
Heterocyclophanes	290	(7)
Multi-layered Cyclophanes	297	(1)
Donor--Acceptor Cyclophanes	298	(9)
Donor--Acceptor Substituted [n.n]Paracyclophanes	298	(2)
[n.n]Paracyclophane Quinhydrones	300	(3)
[n.n]Metacyclophane Quinhydrones	303	(1)
Oligooxa[m.n]paracyclophane Quinhydrones and Related Compounds	304	(1)
Donor--Acceptor Substituted [n.n]Cyclophanes with Extensive π-Electron Systems	305	(2)
References	307	(4)
Electronic Circular Dichroism of Cyclophanes	311	(26)
Stefan Grimme
Arnold Bahlmann
Introduction	311	(1)
Theoretical Methods	312	(2)
Excited States of Model Compounds	314	(9)
Boat-type Deformation in Benzene	314	(5)
Interacting Benzene Fragments	319	(4)
Theoretical and Experimental CD Spectra of Cyclophanes	323	(11)
[n]Cyclophanes	323	(1)
9,12-Dimethyl-4-oxa[7]paracyclophane	323	(1)
[6]Paracyclophane-8-carboxylic Acid	324	(1)
[2.2]Paracyclophanes	325	(1)
[2.2]Paracyclophane	325	(2)
4-Fluoro-[2.2]paracyclophane	327	(2)
4-Methyl[2.2]paracyclophane	329	(2)
[2.2]Metacyclophanes	331	(1)
1-Thia[2.2]metacyclophane	331	(1)
1-Thia-10-aza[2.2]metacyclophane	332	(1)
Cyclophanes with Two Different Aromatic Rings	333	(1)
14,17-Dimethyl[2](1,3)azuleno[2]paracyclophane	333	(1)
Conclusions	334	(1)
Acknowledgement	335	(1)
References	335	(2)
Fully Conjugated Beltenes (Belt-Like and Tubular Aromatics)	337	(22)
Rainer Herges
Introduction	337	(4)
Approaches Towards Fully-Conjugated Beltenes	341	(1)
Belt-like Benzoannulenes (8)	342	(2)
[On]Paracyclophanes 7	344	(10)
Mobius Belts	354	(1)
Conjugated Belts from Fullerenes	355	(1)
References	356	(3)
Molecular Electrochemistry of Cyclophanes	359	(22)
Bernd Speiser
Introduction	359	(2)
Electron Transfer and Molecular Electrochemistry	359	(1)
Molecular Electrochemistry of Cyclophanes	359	(1)
Methods of Molecular Electrochemistry	360	(1)
Molecular Electrochemistry of Hydrocarbon Cyclophanes	361	(2)
Molecular Electrochemistry of Functionalized Cyclophanes	363	(4)
Substituted Cyclophanes	363	(1)
Cyclophanes with Non-metallic Heteroatoms as Ring Members	364	(3)
Molecular Electrochemistry of Organometallic Cyclophane Derivatives	367	(9)
A Possible Classification of Organometallic Cyclophane Derivatives	367	(1)
Metallocenophanes and Metallametallocenophanes	367	(3)
Cyclophanes as π-Complex Ligands	370	(4)
Cyclophanes as Supramolecular Components	374	(2)
Conclusions	376	(1)
References	376	(5)
NMR Spectra of Cyclophanes	381	(34)
Ludger Ernst
Kerstin Ibrom
Introduction and Scope	381	(1)
[n]Phanes	382	(7)
[n]Metacyclophanes	382	(3)
[n]Paracyclophanes	385	(2)
Other [n]Phanes	387	(2)
[2.2]Phanes	389	(7)
[3.3]Phanes	396	(4)
[m.n]Phanes (m>2, n≥2)	400	(6)
[mn]Phanes	406	(3)
Other Phanes	409	(3)
Conclusion	412	(1)
References	412	(3)
Strained Heteroatom-Bridged Metallocenophanes	415	(20)
Ian Manners
Ulf Vogel
Introduction	415	(1)
Synthesis and Structure	416	(6)
[1]Ferrocenophanes	416	(1)
Group 13 Bridged [1]Ferrocenophanes	417	(1)
Group 14 Bridged [1]Ferrocenophanes	417	(2)
Group 15 Bridged [1]Ferrocenophanes	419	(1)
Group 16 Bridged [1]Ferrocenophanes	419	(1)
Other [1]Metallocenophanes	419	(1)
[2]Ferrocenophanes	420	(2)
Other [2]Metallocenophanes	422	(1)
Ring-Opening Polymerization of Strained Ferrocenophanes	422	(4)
Stoichiometric Insertion and Ring-Opening Reactions	422	(1)
Ring-Opening Polymerizations (ROP)	423	(1)
Thermal ROP	423	(1)
Living Anionic ROP of Silicon-Bridged [1]Ferrocenophanes	424	(1)
Transition Metal-Catalyzed ROP of [1]Ferrocenophanes	425	(1)
Other Initiation Methods for ROP	426	(1)
Properties and Applications of Ring-Opened Polyferrocenes	426	(5)
Polyferrocenylsilanes	426	(4)
Other Polymetallocenes via ROP	430	(1)
References	431	(4)
Cyclophanes as Templates in Stereoselective Synthesis	435	(28)
Valeria Rozenberg
Elena Sergeeva
Henning Hopf
Introduction	435	(1)
Chiral [2.2]Paracyclophanes: Nomenclature and Stereochemical Assignment	435	(2)
The Resolution of Representative Mono- and Disubstituted [2.2]Paracyclophanes	437	(1)
Monosubstituted [2.2]Paracyclophanes as Chiral Inductors	437	(3)
Disubstituted [2.2]Paracyclophanes as Chiral Inductors	440	(14)
Ortho- and syn-latero-Substituted Derivatives	440	(9)
Pseudo-ortho-Derivatives	449	(3)
Pseudo-gem-Derivatives	452	(2)
Chiral Templates from Substituted [2.2]Paracyclophanes as Building Blocks	454	(3)
Stereoselective Reactions in the Side Chain of the Paracyclophanyl Moiety	457	(1)
Concluding Remarks	458	(1)
References	459	(4)
Vapor-Based Polymerization of Functionalized [2.2]Paracyclophanes: A Unique Approach towards Surface-Engineered Microenvironments	463	(22)
Doris Klee
Norbert Weiss
Jorg Lahann
Introduction	463	(1)
Synthesis of Functionalized [2.2]Paracyclophanes	464	(2)
CVD Polymerization of Functionalized [2.2]Paracyclophanes	466	(6)
Immobilization of Bioactive Substances via Functionalized Poly(p-xylylenes)	472	(9)
Introduction	472	(3)
Surfaces for Blood Contact	475	(1)
Surfaces for Tissue Contact	476	(2)
Surface Engineering of Microfluidic Devices	478	(3)
Conclusions	481	(1)
References	482	(3)
From Cyclophanes to Molecular Machines	485	(34)
Amar H. Flood
Yi Liu
J. Fraser Stoddart
Introduction	485	(1)
Control over the Location and Motion of Moving Parts in Molecular Machines	485	(1)
The Creation of the Tetracationic Cyclophane	486	(2)
Host--Guest Chemistry with the Tetracationic Cyclophane	488	(4)
Location Control: Host--Guest Chemistry	488	(4)
Catenane Chemistry with the Tetracationic Cyclophane	492	(5)
Going for Gold -- The Story of Olympiadane	495	(2)
Rotaxane Chemistry with the Tetracationic Cyclophane	497	(2)
Location Control -- Catenanes and Rotaxanes	499	(1)
Switchable Rotaxanes, Catenanes and Pseudorotaxanes	499	(6)
Controllable Molecular Shuttles	500	(2)
Switchable Catenanes	502	(1)
Switchable Rotaxanes	503	(1)
Photochemically Switchable Pseudorotaxanes	503	(1)
Control of Motion	504	(1)
Electronic Devices Containing Molecular Switches	505	(8)
A [2]Catenane-Based Electronic Device	506	(2)
Bistable [2]Rotaxane Electronic Devices	508	(2)
Memory Devices	510	(1)
Miniaturization of the Crossbar	510	(3)
Mechanical Devices with Molecular Machines	513	(2)
Conclusions	515	(1)
References	516	(3)
Molecular Recognition Studies with Cyclophane Receptors in Aqueous Solutions	519	(28)
Francois Diederich
Introduction	519	(1)
Complexation of Aromatic Solutes	520	(7)
Polar Effects in Cyclophane Complexation	520	(1)
Complexation of Polycyclic Aromatic Hydrocarbons (PAHs) in Water	521	(2)
The Combination of Apolar Binding and Ion Pairing Leads to Very High Substrate Selectivity	523	(2)
Solvent Dependency of Cyclophane-Arene Complexation and the Nonclassical Hydrophobic Effect: Enthalpic Driving Forces in Aqueous Solution	525	(2)
Steroid Recognition by Cyclophane Receptors	527	(9)
The Search for Cyclophanes with Larger Preorganized Cavity-Binding Sites	527	(2)
Steroid Complexation by Cyclophanes 9 and 10	529	(4)
Double-decker Cyclophanes for Efficient Steroid Complexation: Dissolution of Cholesterol in Water	533	(3)
Catalytic Cyclophanes	536	(5)
Dendritically Encapsulated Cyclophanes (Dendrophanes)	541	(2)
Conclusions	543	(1)
Acknowledgments	543	(1)
References	544	(3)
Subject Index	547