Handbook of Metathesis, 3 Volume Set

by Grubbs, Robert H.

• ISBN13: 9783527306169
• ISBN10: 3527306161
• Edition: 1st
• Format: Hardcover
• Copyright: 2003-10-17
• Publisher: Wiley-VCH

Summary

There is probably no name more closely linked to metathesis than that of Robert H. Grubbs of the California Institute of Technology. His pioneering work has led to the success of this important and fascinating reaction and in this comprehensive three-volume work he presents all its important aspects. The standard work on the topic The team of authors reads like a "Who's who" of metathesis Clearly divided into catalyst developments, organic synthesis applications and polymer synthesis A must-have for every organic and polymer chemist

Author Biography

Robert H. Grubbs received his Ph.D. from Columbia University for work with Ron Breslow. After a postdoctoral year with Jim Collman at Stanford University, he joined the faculty at Michigan State University. In 1978, he moved to the California Institute of Technology, where he is now the Victor and Elizabeth Atkins Professor of Chemistry. Among many other awards he received the Nobel Prize in 2005 for his research on the metathesis reaction. His research interests include polymer chemistry, organometallic catalysis, and development of new synthetic organic methodology.

Table of Contents

Preface	xxi
References	xxv
List of Contributors	xxvii
Introduction	1	(3)
Robert H. Grubbs
References	3	(1)
The Role of the ``Tebbe Complex'' in Olefin Metathesis	4	(4)
Robert H. Grubbs
References	6	(2)
The Discovery and Development of High Oxidation State Mo and W Imido Alkylidene Complexes for Alkene Metathesis	8	(25)
Richard R. Schrock
Introduction	8	(1)
Tantalum Alkylidene Complexes	9	(4)
Early Tungsten Alkylidene Complexes	13	(2)
Development of Imido Alkylidene Complexes	15	(5)
Rhenium Alkylidene Complexes	20	(1)
Details of Reactions of Imido Alkylidene Complexes and Theoretical Calculations	21	(3)
Catalyst and Reaction Variations	24	(4)
Concluding Remarks	28	(5)
Acknowledgments	28	(1)
References	29	(4)
From III-Defined to Well-Defined W Alkylidene Complexes	33	(14)
Christophe Coperet
Frederic Lefebvre
Jean-Marie Basset
Introduction	33	(1)
Oxoalkylidene W Complexes	33	(2)
Alkoxy-Alkylidene W Complexes: Kress-Osborn System	35	(2)
Aryloxy-Alkylidene W Complexes: Leconte-Basset System	37	(1)
Amidoalkylidene W Complexes	38	(4)
Imido-Alkylidene W Complexes: Schrock's System	42	(2)
Summary and Outlooks	44	(3)
References	45	(2)
Fischer Metal Carbenes and Olefin Metathesis	47	(14)
Thomas J. Katz
Fischer Metal Carbenes and Olefin Metathesis	47	(1)
The Role of Fischer Metal Carbenes in Metathesis	47	(2)
Induction of Olefin Metatheses by Fischer Metal Carbenes	49	(4)
Properties of 2	49	(1)
Olefin Metatheses Initiated by Metal Carbene 1	49	(2)
Mechanistic Implications	51	(1)
Metatheses Initiated by Metal Carbene 2	52	(1)
Initiation of Acetylene Polymerization by Fischer Metal Carbenes	53	(2)
Introduction	53	(1)
Examples of Acetylene Polymerizations Initiated by Fischer Metal Carbenes	54	(1)
Actuation of Olefin Metathesis by Acetylenes	55	(6)
Metatheses of Cyclic and Acyclic Alkenes Actuated by An Acetylene	55	(1)
Reaction of Enynes With Fischer Metal Carbenes	55	(1)
Rearrangement of Enynes to Dienes	56	(1)
References	57	(4)
The Discovery and Development of Well-Defined, Ruthenium-Based Olefin Metathesis Catalysts	61	(25)
SonBinh T. Nguyen
Tina M. Trnka
The Discovery of Well-Defined Ruthenium Olefin Metathesis Catalysts: A Personal Account	61	(4)
SonBinh Nguyen
(PPh3)2 Cl2 Ru=CH-CH=CPh2, the First Well-Defined, Metathesis-Active Ruthenium Alkylidene Complex	62	(1)
(PCy3)2 Cl2 Ru=CH-CH=CPh2, A Well-Defined Ruthenium Alkylidene Catalyst for the Metathesis of Acyclic Olefins	63	(1)
Initial Applications of Olefin Metathesis Chemistry Catalyzed by (PCy3)2 Cl2 Ru=CH-CH=CPh2	64	(1)
More Accessible Ruthenium Alkylidene Sources	65	(3)
2nd-Generation Grubbs Catalysts	68	(5)
N-Heterocyclic Carbene (NHC) Ligands	70	(3)
Multi-Component Ruthenium-Based Olefin Metathesis Catalyst Systems and Homogeneous Catalyst Precursors	73	(1)
Solid-Supported Ruthenium-Based Olefin Metathesis Catalysts	74	(6)
Conclusions	80	(6)
References	81	(5)
Synthesis of Ruthenium Carbene Complexes	86	(9)
Warren R. Roper
Introduction	86	(1)
The First Ruthenium Carbene Complexes	86	(2)
Ruthenium Methylene Complexes	88	(4)
Ruthenium Dihalocarbene Complexes	92	(3)
Acknowledgments	93	(1)
References	93	(2)
Synthesis of Rhodium and Ruthenium Carbene Complexes with a 16-Electron Count	95	(17)
Helmut Werner
Justin Wolf
Introduction	95	(1)
Rhodium(I) Carbenes from Diazoalkanes	95	(3)
Ruthenium(II) Carbenes and Vinylidenes from Terminal Alkynes	98	(10)
Conclusions	108	(4)
Acknowledgements	109	(1)
References	109	(3)
Mechanism of Ruthenium-Catalyzed Olefin Metathesis Reactions	112	(20)
Melanie S. Sanford
Jennifer A. Love
Introduction	112	(1)
First-Generation Bis-Phosphine Catalyst Systems	112	(11)
General Mechanistic Considerations	112	(4)
Substituent Effects in Ruthenium-Catalyzed Olefin Metathesis	116	(2)
Thermal Decomposition of Ruthenium Catalysts	118	(2)
Decomposition in the Presence of Functional Groups	120	(1)
Mechanistic Considerations in Other First-Generation Ruthenium Metathesis Catalysts	120	(3)
Second-Generation Ruthenium Olefin Metathesis Catalysts	123	(6)
General Mechanistic Considerations	124	(1)
Substituent Effects in Ruthenium-Catalyzed Olefin Metathesis	125	(2)
Thermal Decomposition of Ruthenium Catalysts	127	(1)
Decomposition in the Presence of Functional Groups	127	(1)
Other Second-Generation Ruthenium Catalysts	128	(1)
Conclusions	129	(3)
References	130	(2)
Intrinsic Reactivity of Ruthenium Carbenes	132	(41)
Christian Adlhart
Peter Chen
Introduction	132	(3)
Electrospray Ionization Mass Spectrometry (ESI MS) of Transition Metal Complexes	135	(4)
Electrospray Ionization	135	(1)
Tandem Mass Spectrometry	136	(1)
Reaction Conditions in the Collision Cell of the Tandem ESI MS	137	(2)
General Reactivity of Ruthenium Carbene Complexes in the Gas Phase	139	(8)
Dissociative Mechanism	139	(2)
Evidence for ROMP and RCM	141	(2)
Systematic Variation of a Common Structural Motif -- Steric Effects and Halogen Effects	143	(3)
Conclusions	146	(1)
Three Key Factors that Determine the Activity of Metathesis Catalysts	147	(20)
Solution-Phase Pre-Equilibria: Activation	147	(1)
Pre-Equilibria During the Turnover: Backbiting	148	(7)
Catalyst Commitment: Potential Surface	155	(12)
Conclusions	167	(6)
Compound Numbers	167	(2)
References	169	(4)
The Discovery and Development of High Oxidation State Alkylidyne Complexes for Alkyne Metathesis	173	(17)
Richard R. Schrock
Introduction	173	(1)
Alkylidyne Complexes of Tantalum	174	(1)
Alkylidyne Complexes of Tungsten	174	(4)
Formation of Trialkoxy Alkylidyne Complexes from W2(OR)6 Species	178	(2)
Alkylidyne Complexes of Molybdenum	180	(1)
Reactions that Limit Metathesis Activity	181	(4)
Alkylidyne Complexes of Rhenium	185	(1)
Conclusions and Comments	186	(4)
Acknowledgments	187	(1)
References	187	(3)
Well-Defined Metallocarbenes and Metallocarbynes Supported on Oxide Supports Prepared via Surface Organometallic Chemistry: A Source of Highly Active Alkane, Alkene, and Alkyne Metathesis Catalysts	190	(1)
Christophe Coperet
Frederic Lefebvre
Jean-Marie Basset
Introduction	190	(1)
Preparation and Characterization of Well-Defined Metallocarbenes and Metallocarbynes via Surface Organometallic Chemistry	191	(4)
Strategy and Tools in Surface Organometallic Chemistry	191	(1)
Application to the Preparation of Well-Defined Metallocarbene and Metallocarbyne Supported on Oxides	192	(3)
Reactivity in Alkene and Alkyne Metathesis	195	(5)
Group 5 and 6 Metallocarbenes and Metallocarbynes Supported on Oxides	195	(2)
Group 7 Metallocarbenes and Metallocarbynes Supported on Oxides	197	(3)
Reactivity in Alkane Metathesis	200	(1)
Summary and Outlook	201	(1)
Acknowledgments	202	(1)
References	202
List of Contributors	xxi
Olefin Metathesis and Related Reactions in Organic Synthesis: Introduction to Metal-Carbon Double Bonds in Organic Synthesis	1	(4)
Robert H. Grubbs
References	4	(1)
General Ring-Closing Metathesis	5	(123)
So-Yeop Han
Sukbok Chang
Introduction	5	(2)
Synthesis of Carbocyles	7	(17)
Carbocyclization	7	(9)
Medium-Sized Carbocycles	16	(6)
Spiro Carbocycles	22	(2)
Synthesis of Bridged Bicycloalkenes	24	(5)
Synthesis of Heterocycles Containing Si, P, S, or B	29	(9)
Si-Heterocycles	29	(3)
P-Heterocycles	32	(3)
S-Heterocycles	35	(2)
B-Heterocycles	37	(1)
Synthesis of Cyclic Ethers	38	(8)
Mono- and Bicyclic Ethers	38	(5)
Polycyclic Ethers	43	(3)
Applications to N-Heterocycles and Peptide Chemistry	46	(19)
N-Heterocycles	46	(6)
Small and Medium-Sized Lactams	52	(2)
Cyclic Amino Acids, Peptides, and Peptidomimetics	54	(11)
Synthesis of Macrocycles	65	(9)
Macrocycles	66	(2)
Macrolactones	68	(5)
Macrolactams	73	(1)
Synthesis of Cyclic Conjugated Dienes	74	(3)
Alkyne Metathesis	77	(3)
Enyne Metathesis	80	(6)
General Enyne Metathesis	80	(3)
Dienyne Metathesis	83	(3)
Multi-Directional RCM	86	(2)
Tandem Processes	88	(6)
Tandem ROM/RCM	88	(4)
Other Tandem RCM	92	(2)
Asymmetric RCM	94	(2)
Synthesis of Complex Molecules	96	(32)
Template-Directed RCM	96	(1)
RCM in Supramolecular Chemistry	96	(13)
Synthetic Applications	109	(10)
References	119	(9)
Catalytic Asymmetric Olefin Metathesis	128	(23)
Amir H. Hoveyda
Introduction	128	(1)
The Catalyst Construct	129	(1)
Mo-Catalyzed Kinetic Resolution With Hexafluoro-Mo Catalysts	129	(1)
Chiral Mo-Diolate Complexes for Kinetic Resolution and Asymmetric Synthesis	130	(15)
Chiral Biphen-Mo Catalysts	130	(1)
Catalytic Kinetic Resolution Through Mo-Catalyzed ARCM	130	(1)
Catalyst Modularity and Optimization of Mo-Catalyzed ARCM Efficiency and Selectivity	131	(2)
Catalytic Asymmetric Synthesis Through Mo-Catalyzed ARCM	133	(4)
Catalytic Asymmetric Synthesis Through Tandem Mo-Catalyzed AROM/RCM	137	(5)
Catalytic Asymmetric Synthesis Through Tandem Mo-Catalyzed AROM/CM	142	(1)
Towards User-Friendly and Practical Chiral Mo-Based Catalysts for Olefin Metathesis	143	(2)
Chiral Ru-Based Olefin Metathesis Catalysts	145	(2)
Conclusions and Outlook	147	(4)
Acknowledgments	148	(1)
References	148	(3)
Tandem Ring-Closing Metathesis	151	(25)
Stefan Randl
Siegfried Blechert
Introduction	151	(1)
Tandem Metathesis Involving Double Bonds Only	152	(12)
RRM of Alkenyl-Substituted Cycloolefins	152	(8)
RRM of bis Alkenyl-Substituted Cycloolefins	160	(4)
Tandem Reactions of Polycycloolefins	164	(1)
Tandem RCM Involving Enyne Reactions	164	(8)
Tandem Reactions with Triple Bonds As ``Relays''	164	(2)
Tandem Processes Involving Ring Rearrangement	166	(3)
Alkyne Trimerizations Catalyzed by Metathesis Catalysts	169	(2)
Other Tandem Processes Involving C--C Triple Bonds	171	(1)
Summary and Outlook	172	(4)
References	173	(3)
Ene-Yne Metathesis	176	(29)
Miwako Mori
Introduction	176	(4)
Transition Metal-Carbene Complex-Catalyzed Enyne Metathesis	180	(14)
Ring-Closing Metathesis (RCM) of Enyne Using Ruthenium Carbene Complex	180	(6)
Ring-Opening Metathesis--Ring-Closing Metathesis of Cycloalkene-Yneo	186	(2)
Intermolecular Enyne Metathesis (Cross-Metathesis)	188	(6)
Skeletal Reorganization Using Transition Metals	194	(4)
Utilization of Enyne Metathesis for the Synthesis of Natural Products and Related Biologically Active Substances	198	(2)
Perspective	200	(5)
References	203	(2)
Ring-Opening Cross-Metatheses	205	(33)
Thomas O. Schrader
Marc L. Snapper
Introduction	205	(1)
Early Examples of ROCM	206	(7)
Mechanistic Insight	206	(1)
Early Efforts toward a Selective ROCM	207	(2)
Well-Defined Metal Complexes as Catalysts	209	(3)
New Opportunities for Olefin Metathesis	212	(1)
Selective ROCM Reactions	213	(15)
ROCM Involving Cyclobutenes	213	(3)
Regio- and Stereoselective ROCM	216	(2)
ROCM of Bridged Bicyclic Alkenes	218	(5)
ROCM Reactions of Cyclopropenes	223	(1)
ROCM Reactions Involving Unstrained Cycloolefins	224	(1)
ROCM Reactions of Trisubstituted Olefins	224	(2)
Variations of ROCM	226	(1)
Ring Expansion via Olefin Metathesis	226	(2)
Enantioselective ROCM	228	(2)
Mo-Catalyzed Asymmetric ROCM	228	(2)
A Recyclable Chiral Ruthenium Catalyst for Asymmetric ROCM	230	(1)
ROCM in Total Synthesis	230	(3)
Conclusions	233	(5)
References	235	(3)
Ring-Expansion Metathesis Reactions	238	(8)
Choon Woo Lee
References	244	(2)
Olefin Cross-Metathesis	246	(50)
Arnab K. Chatterjee
Olefin Forming Cross-Coupling Reactions	246	(1)
Olefin Metathesis and Selectivity Problems in CM	247	(2)
Metathesis Catalyst Overview	249	(1)
Selectivity Challenges in CM	250	(2)
Stereoselective CM Reactions	252	(4)
Product-Selective Reactions by CM	256	(2)
Styrene CM Reactions	258	(3)
Trisubstituted Olefin Synthesis by CM	261	(3)
Electron-Poor Olefins in CM	264	(5)
Reagent Synthesis by CM	269	(6)
Applications of CM	275	(3)
Bioorganic Applications of CM	278	(10)
CM Product-Selectivity Model	288	(2)
Conclusions	290	(6)
References	292	(4)
Olefin Metathesis Strategies in the Synthesis of Biologically Relevant Molecules	296	(27)
Jennifer A. Love
Introduction	296	(2)
Olefin Metathesis Strategies in Complex Molecule Synthesis	296	(1)
Catalysts for Olefin Metathesis	297	(1)
RCM and ROM in Complex Molecule Synthesis	298	(14)
Laulimalide	298	(4)
Boronolide	302	(1)
Ingenol	303	(1)
Asteriscanolide	303	(2)
(+)-FR900482	305	(1)
Salicylihalamide	306	(1)
Roseophilin	307	(2)
Ircinal A and Manzamine A	309	(1)
Amphidinolide A	309	(1)
Peptidomimetics	310	(2)
Ring-Closing Ene-Yne Metathesis	312	(2)
Cross-Metathesis in the Synthesis of Complex Molecules	314	(2)
( -- )-Cylindrocyclophanes A and F	314	(1)
Garsubellin A	315	(1)
(+)-Brefeldin A	315	(1)
ROMP in Complex Molecule Synthesis	316	(2)
Conclusions	318	(5)
References	319	(4)
Vignette 1 The Olefin Metathesis Reaction in Complex Molecule Construction	323	(15)
K. C. Nicolaou
Scott A. Snyder
Acknowledgments	334	(1)
References	335	(3)
Vignette 2 Applications of Ring-Closing Metathesis to Alkaloid Synthesis	338	(15)
Stephen F. Martin
Introduction	338	(1)
Methodological Studies	339	(3)
Synthesis of Alkaloid Natural Products	342	(8)
Conclusions	350	(1)
Acknowledgments	351	(1)
References	351	(2)
Vignette 3 Radicicol and the Epothilones: Total Synthesis of Novel Anticancer Agents Using Ring-Closing Metathesis	353	(8)
Jon T. Njardarson
Robert M. Garbaccio
Samuel J. Danishefsky
References	359	(2)
The Use of Olefin Metathesis in Combinatorial Chemistry: Supported and Chromatography-Free Syntheses	361	(42)
Andrew M. Harned
Donald A. Probst
Paul R. Hanson
Introduction	361	(1)
Metathesis Reactions Toward Supported Synthesis and Library Generation	362	(13)
Ring-Closing Metathesis (RCM)	362	(7)
Cross-Metathesis (X-MET)	369	(6)
Polymer-Supported Metathesis Catalysts	375	(2)
ROMP-Based Strategies	377	(19)
ROMPgel Reagents	378	(8)
ROMP as a Purification Tool	386	(4)
ROMPspheres	390	(1)
ROM Polymers as Supports	391	(5)
Conclusions	396	(7)
Acknowledgements	399	(1)
References	399	(4)
Metal-Catalyzed Olefin Metathesis in Metal Coordination Spheres	403	(29)
Eike B. Bauer
J. A. Gladysz
Introduction	403	(1)
Earliest Literature	404	(1)
Ferrocenes	405	(5)
Sophisticated Target Molecules: Catenanes and Knots	410	(4)
Systematic Investigation of Reaction Scope	414	(6)
Additional Literature Examples	420	(5)
Towards Additional Types of Sophisticated Target Molecules	425	(4)
Summary	429	(1)
Addendum	429	(3)
Acknowledgments	429	(1)
References	430	(2)
Alkyne Metathesis	432	(31)
Alois Furstner
Introduction	432	(1)
Classical Catalyst Systems for Alkyne Metathesis	432	(2)
Recent Advances in Catalyst Design	434	(3)
Preparative Applications of Alkyne Metathesis	437	(21)
Alkyne Homometathesis Reactions	437	(2)
Alkyne Cross-Metathesis	439	(4)
Ring-Closing Alkyne Metathesis (RCAM)	443	(5)
Applications of RCAM to Natural Product Synthesis	448	(8)
Post-Metathesis Transformations Other Than Lindlar Hydrogenation: Selective Synthesis of (E)-Alkenes and Heterocyclic Motifs	456	(2)
Conclusions and Outlook	458	(5)
References	459	(4)
Metathesis of Silicon-Containing Olefins	463	(28)
Bogdan Marciniec
Cezary Pietraszuk
Introduction	463	(1)
Self-Metathesis of Alkenylsilanes	464	(1)
Cross-Metathesis vs. Silylative Coupling (Trans-Silylation) of Alkenes with Vinylsilanes	464	(6)
Cross-Metathesis of Allylsilanes with Alkenes	470	(2)
Ring-Closing Metathesis of Silicon-Containing Dienes	472	(4)
Ring-Opening Metathesis/Cross-Metathesis	476	(2)
Polycondensation vs. Ring Closing of Divinyl-Substituted Silicon Compounds	478	(3)
ADMET Polymerization of Silicon-Containing Dienes	481	(2)
Ring-Opening Metathesis Polymerization of Silacycloalkenes	483	(1)
Ring-Opening Metathesis Polymerization of Silyl-Substituted Cycloalkenes	483	(2)
Degradation vs. Functionalization of Polymers	485	(6)
References	486	(5)
Commercial Applications of Ruthenium Metathesis Processes	491	(1)
Richard L. Pederson
Introduction	491	(1)
Fine Chemicals	491	(4)
Agrochemicals: Insect Pheromones	492	(2)
Polymer Additives	494	(1)
Fuel Additives	494	(1)
Drug Discovery	494	(1)
Pharmaceutical Applications	495	(10)
Future Directions for Metathesis	505	(1)
Summary	506	(1)
References	507
List of Contributors	xxi
Introduction	1	(1)
Robert H. Grubbs
Living Ring-Opening Olefin Metathesis Polymerization	2	(70)
Grainne Black
Declan Maher
Wilhelm Risse
Historic Overview of Living Polymerization Systems	2	(2)
Definition of Living Polymerization and Relevant Terminology	4	(2)
Introduction to ROMP	6	(5)
Olefin Metathesis Catalysts for Living Polymerizations	11	(61)
Titanacyclobutane Compounds	11	(5)
Tantalum-Alkylidene and Tantalacyclobutane Complexes for Norbornene Polymerizations	16	(1)
Tungsten Catalysts	17	(4)
Imido Molybdenum-Alkylidene Complexes	21	(12)
Imido Tungsten- and Molybdenum-Alkylidene Catalysts for ROMP of Monomers Containing Cyclobutene, Bicyclooctadiene, and Bicyclooctadiene Ring Systems	33	(9)
Tungsten- and Molybdenum-Alkylidene Catalysts in Cyclopentene Polymerizations	42	(1)
Paracyclophene Polymerizations	43	(1)
Ruthenium Catalysts and Living ROMP	44	(19)
Star-Shaped Polymers via ROMP	63	(3)
References	66	(6)
Synthesis of Copolymers	72	(46)
Ezat Khosravi
Introduction	72	(1)
Random Copolymers	72	(4)
Block Copolymers	76	(16)
Sequential Addition of Monomers	76	(7)
Coupling Reaction	83	(1)
Transformation of Propagating Species	84	(6)
Application of Well-Defined Bimetallic Initiators	90	(2)
Comb and Graft Copolymer	92	(6)
Combination of ROMP and Anionic Polymerization	92	(2)
Combination of ROMP and ATRP	94	(1)
Combination of ROMP and Cationic Polymerization	95	(1)
Combination of ROMP and Wittig-Type Reaction	96	(1)
Repetitive ROMP	96	(2)
Multi-Shaped Copolymers	98	(5)
Alternating Copolymers	103	(2)
Cross-Linked Copolymers	105	(13)
Well-Defined, Cross-Linked System via Direct Copolymerization	105	(5)
Cross-Linked Systems via Homopolymerization of Monomers with Cross-Linkable Side Chains	110	(2)
Cross-Linked Material via Combination of ROMP and Oxidative Polymerization	112	(1)
References	113	(5)
Conjugated Polymers	118	(25)
W. James Feast
Introduction	118	(3)
Strategies for Applying ROMP in the Synthesis of Conjugated Polymers	121	(1)
Direct Routes from Monomer to Conjugated Polymer Via Chain-Growth Processes	122	(5)
Direct Routes from Monomer to Conjugated Polymer Via Step-Growth Processes	127	(2)
Indirect Routes to Conjugated Polymer Via Processable Precursor Polymers	129	(10)
Conclusions	139	(4)
References	139	(4)
Stereochemistry of Ring-Opening Metathesis Polymerization	143	(37)
James G. Hamilton
Introduction	143	(1)
Consequences of cis/trans Isomerism and Tacticity in ROMP Polymers	144	(2)
Determination of the Stereochemistry of ROMP Polymers	146	(10)
Cis/trans Double-Bond Ratio	146	(3)
Tacticity	149	(7)
Control and Interpretation of Stereochemistry	156	(24)
Ratio and Distribution of cis and trans Double Bonds	156	(13)
Tacticity	169	(7)
References	176	(4)
Syntheses and Applications of Bioactive Polymers Generated by Ring-Opening Metathesis Polymerization	180	(46)
Laura L. Kiessling
Robert M. Owen
Introduction	180	(3)
Synthesis of Biologically Active Polymeric Displays	183	(20)
Carbohydrate-Containing Polymeric Displays	183	(6)
Peptide-Substituted Polymers	189	(4)
Synthesis of DNA/Polymer Conjugates via ROMP	193	(2)
Synthesis of Drug/Polymer Conjugates via ROMP	195	(1)
Post-Polymerization Modification Strategies	196	(3)
End-Capping Strategies	199	(4)
Applications of Biologically Active Polymeric Displays	203	(17)
Protein-Carbohydrate Interactions	203	(8)
Integrins and Cellular Adhesion	211	(2)
Pathogenic Organisms	213	(3)
Cell Clustering	216	(1)
Bacterial Chemotaxis	216	(4)
Conclusions	220	(6)
References	222	(4)
Metathesis Polymerization: A Versatile Tool for the Synthesis of Surface-Functionalized Supports and Monolithic Materials	226	(29)
Michael R. Buchmeiser
Introduction	226	(1)
Precipitation Polymerization-Based Techniques	226	(4)
Grafting Techniques	230	(9)
Coating Techniques	239	(1)
Monolithic Supports	240	(11)
Basics and Concepts	241	(1)
Manufacture of Metathesis-Based Monolithic Supports	242	(1)
Microstructure of Metathesis-Based Rigid Rods	242	(3)
Functionalization, Metal Removal, and Metal Content	245	(2)
Applications of Functionalized Metathesis-Based Monoliths in Catalysis	247	(4)
Conclusions, Summary, and Outlook	251	(4)
Acknowledgments	251	(1)
References	251	(4)
Telechelic Polymers from Olefin Metathesis Methodologies	255	(28)
Christopher W. Bielawski
Marc A. Hillmyer
Introduction and Background	255	(3)
Telechelic Polymers from Metathesis Polymerizations	258	(5)
Molecular Weight and Functionality Control in a ROMP/CT System	260	(3)
Syntheses and Applications of Telechelic Polymers Prepared Using Metathesis	263	(16)
Synthesis of Telechelic Polymers Using Ill-Defined Catalysts	264	(3)
Synthesis of Telechelic Polymers Using Well-Defined Metal Alkylidenes	267	(10)
Synthesis of End-Functionalized Polymers Using Functionalized Initiators	277	(2)
Conclusions and Outlook	279	(4)
References	280	(3)
ADMET Polymerization	283	(71)
Stephen E. Lehman, Jr.
Kenneth B. Wagener
Introduction	283	(5)
ADMET: The Metathesis Polycondensation Reaction	288	(6)
Kinetics and Equilibrium Considerations	289	(2)
Molecular Weight Distribution	291	(1)
Interchange Reactions	291	(1)
Cyclization vs. Polymerization	292	(1)
Monomer Purity	293	(1)
Early Observations in the Evolution of ADMET Polymerization: Reactions of Non-Conjugated Dienes with Classical Metathesis Catalysts	294	(3)
ADMET of Non-Conjugated Hydrocarbon Dienes with Well-Defined Metathesis Catalysts	297	(13)
Linear Terminal Dienes	297	(3)
Branched Terminal Dienes	300	(5)
Geminal Disubstituted Olefins	305	(2)
1,2-Disubstituted Olefins	307	(1)
Trisubstituted Olefins	308	(2)
ADMET Copolymerization	310	(1)
Synthesis of Conjugated Polymers via ADMET	311	(5)
Polyacetylenes	311	(2)
Polyphenylenevinylenes	313	(2)
Other Conjugated Polymers	315	(1)
ADMET Polymerization of Functionalized Dienes	316	(13)
Ethers, Acetals, and Alcohols	318	(1)
Amines	319	(1)
Boronates	320	(1)
Thioethers	321	(1)
Carbonyl Compounds	322	(3)
Halides	325	(1)
Silicon Compounds	325	(4)
Organometallic Compounds	329	(1)
Retro-ADMET: Towards Recycling of Unsaturated Polymers with Well-Defined Metathesis Catalysts	329	(2)
Telechelic Oligomers via ADMET	331	(1)
Kinetics and Mechanism	332	(6)
Modeling Polyolefins with ADMET	338	(7)
Hydrogenation of ADMET Polymers	338	(1)
Branched Polyethylene	339	(3)
Functionalized Polyethylene	342	(3)
Towards Biologically Useful Polymers via ADMET	345	(2)
Solid-State Polymerization	347	(1)
Conclusions and Outlook	347	(7)
References	347	(7)
Acyclic Diyne Metathesis Utilizing in Situ Transition Metal Catalysts: An Efficient Access to Alkyne-Bridged Polymers	354	(21)
Uwe H. F. Bunz
Introduction	354	(3)
Alkyne Metathesis	355	(2)
ADIMET: Synthesis of Alkyne-Bridged Polymers	357	(13)
Synthesis of PPEs by in situ ADIMET	360	(3)
Synthesis of PPE-PPV Copolymers by in situ ADIMET	363	(2)
Synthesis of Other PAEs by ADIMET	365	(5)
Alkyne-Bridged Carbazole Polymers (PCE) by ADIMET	370	(1)
Conclusions	370	(5)
Acknowledgments	371	(1)
References	371	(4)
Polymerization of Substituted Acetylenes	375	(32)
Toshio Masuda
Fumio Sanda
Introduction	375	(3)
Polymerization Catalysts	378	(6)
Mo and W Catalysts	378	(3)
Nb and Ta Catalysts	381	(1)
Rh Catalysts	382	(2)
Other Group 8--10 Metal Catalysts	384	(1)
Controlled Polymerizations	384	(5)
Living Polymerization by Metal Halide-Based Metathesis Catalysts	385	(2)
Living Polymerization by Single-Component Metal-Carbene Catalysts	387	(1)
Stereospecific Living Polymerization by Rh Catalysts	388	(1)
New Monomers and Functional Polymers	389	(18)
Gas-Permeable Polyacetylenes	396	(1)
Optically Active Polyacetylenes	397	(2)
Other Functional Polyacetylenes	399	(2)
References	401	(6)
Commercial Applications of Ruthenium Olefin Metathesis Catalysts in Polymer Synthesis	407	(12)
Mark S. Trimmer
Introduction	407	(1)
Background	407	(1)
New Developments	408	(1)
Poly-DCPD	409	(2)
Other ROMP Polymers	411	(2)
Hydrogenated ROMP Polymers	413	(1)
Depolymerization	414	(1)
Summary	414	(5)
References	414	(5)
Index	419