Chiral Diazaligands for Asymmetric Synthesis

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Format: Hardcover
Pub. Date: 2005-12-16
Publisher(s): Springer Verlag
List Price: $534.95

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Summary

The use of phosphine derivatives has historically induced the tremendous development of catalysis (both non-asymmetric and asymmetric). Although the chemistry of amines is more documented, the use of nitrogen-containing ligands only appeared recently. Nevertheless, during the last ten years, the results describing chiral diamine preparations and their uses in asymmetric catalysis and synthesis are increasing faster than their phosphorus counterparts. The reader will find in this volume the most recent methods for the synthesis of chiral diamines as well as their applications in asymmetric catalysis of CC bond formation. Particular attention will be given to spartein and derivatives of such diamines. Recently, the particular properties and the chemistry of amines allowed to obtain catalysts easy to separate and recycle and new types of ligands such as diaminocarbenes, ureas and thioureas. Finally, the complexing properties of some diamines allowed the formation of complexes with chirality "at the metal " which is of major theoretical interest and presents numerous potential applications.

Table of Contents

Progress in the Asymmetric Synthesis of 1,2-Diamines from Azomethine Compounds
1(58)
D. Savoia
Introduction
2(2)
Synthesis of 1,2-Diamines from Monoimines
4(40)
Reductive Coupling of Imines
4(1)
Introduction
4(1)
Mechanism
5(1)
Synthesis of C2-Symmetric Acyclic 1,2-Diaryl-Substituted 1,2-Diamines
6(5)
Synthesis of Trisubstituted and Tetrasubstituted Piperazines
11(1)
Perspectives
12(1)
Addition of α-Amino Carbon Nucleophiles to Imines
13(1)
α-Amino Organometallic Reagents
13(3)
α-Nitro Carbanions
16(4)
α-Amino Enolates and α-Amino Silyl Enol Ethers
20(5)
Addition of Carbon Nucleophiles to Chiral α-Amino Azomethine Compounds
25(1)
Addition of Organometallic Reagents
25(7)
Addition of Nitronates, Enolates, Silyl Ketene Acetals and Cyanide Ion
32(3)
Perspectives
35(2)
Reduction of α-Amino Azomethine Compounds
37(1)
Reduction of α-Amino Ketimines
37(1)
Reductive Amination of α-Aminoketones
38(2)
Organometallic Addition/Reduction Sequence on Chiral α-Aminonitriles
40(4)
Synthesis of 1,2-Diamines from 1,2-Diimines and 1,2-Dihydrazones
44(15)
Addition of Organometallic Reagents
44(1)
Glyoxal Diimines
44(6)
Glyoxal Dihydrazones
50(1)
Perspectives
51(1)
Reduction of 1,2-Diketimines
52(1)
Diastereoselective Reduction of Chiral 1,2-Diketimines
52(1)
Enantioselective Reduction of 1,2-Diketimines
53(1)
References
54(5)
Sparteine as a Chiral Ligand for Asymmetric Catalysis
59(34)
O. Chuzel
O. Riant
Introduction
59(1)
Sparteine as a Chiral Ligand for Organolithium Reagents
60(14)
Organolithium Reagents/Sparteine Combinations as Chiral Nucleophiles for Enantioselective Additions
61(9)
Organolithium Reagents: Sparteine as Chiral Bases
70(4)
Sparteine as a Chiral Ligand for Copper Catalysts
74(7)
Stoichiometric Processes with Copper Complexes
74(3)
Catalytic Processes with Copper Complexes
77(4)
Sparteine as a Chiral Ligand for Palladium Catalysts
81(9)
Conclusion
90(3)
References
91(2)
Use of N,N-Coordinating Ligands in Catalytic Asymmetric C--C Bond Formations: Example of Cyclopropanation, Diels--Alder Reaction, Nucleophilic Allylic Substitution
93(56)
E. Schulz
Introduction
94(1)
Asymmetric Cyclopropanation
95(19)
Bis(oxazoline) Ligands
96(1)
Copper Complexes
96(6)
Ruthenium Complexes
102(1)
Rhodium Complexes
103(1)
Bipyridine Copper and Rhodium Complexes
104(3)
Miscellaneous N,N-Containing Copper Complexes
107(2)
Miscellaneous N,N-Containing Ruthenium Complexes
109(1)
Porphyrine-Containing Complexes
109(2)
Heterogeneous Catalysis
111(3)
Conclusion
114(1)
Asymmetric Diels-Alder Reaction
114(19)
Bis(oxazoline) Ligands
115(1)
Copper Complexes
115(6)
Zinc Complexes
121(1)
Ruthenium Complexes
122(1)
Pyridine Bis(oxazoline) and Rare Earth Complexes
123(1)
Miscellaneous N,N-Containing Copper Complexes
124(4)
Miscellaneous N,N-Containing Magnesium Complexes
128(1)
Miscellaneous N,N-Containing Rare Earth Complexes
129(1)
Heterogeneous Catalysis
130(2)
Conclusion
132(1)
Asymmetric Nucleophilic Allylic Substitution
133(10)
Bipyridines, Terpyridines, Phenanthrolines and Related Ligands
134(2)
Oxazolinylpyridines and Related Ligands
136(2)
Bis(oxazoline) Ligands
138(1)
Bis(pyridylamide) Ligands
138(1)
Miscellaneous N,N-Containing Copper Complexes
139(1)
Heterogeneous Catalysis
140(2)
Conclusion
142(1)
Conclusion
143(6)
References
144(5)
Non-covalent Immobilization of Catalysts Based on Chiral Diazaligands
149(42)
J. M. Fraile
J. I. Garcia
J. A. Mayoral
Introduction
150(1)
Methods for Non-covalent Immobilization
150(2)
Liquid-Liquid Systems
151(1)
Solid-Liquid Systems
151(1)
Non-covalently Immobilized Catalysts Based on Chiral Salen Ligands
152(17)
Liquid Phase Immobilization
153(1)
Fluorinated Solvents
153(4)
Ionic Liquids
157(2)
Solid Phase Immobilization
159(1)
Entrapment
159(3)
Adsorption
162(2)
Ion Exchange
164(5)
Non-covalently Immobilized Catalysts Based on Chiral Bis(oxazoline) Ligands
169(14)
Liquid Phase Immobilization
169(1)
Fluorinated Solvents
169(1)
Ionic Liquids
170(3)
Solid Phase Immobilization
173(1)
Cationic Exchange
173(10)
Adsorption
183(1)
Miscellaneous Chiral Ligands
183(4)
Diamines and Related Ligands
183(3)
Porphyrins
186(1)
Natural Aminated Polymers
186(1)
Conclusions
187(4)
References
188(3)
Chiral Diaminocarbene Complexes, Synthesis and Application in Asymmetric Catalysis
191(40)
S. Roland
P. Mangeney
General Introduction
192(1)
Structure of N-heterocyclic Carbenes
192(2)
Synthesis of Chiral N-heterocyclic Carbenes and of Their Complexes
194(11)
Introduction
194(3)
Preparation of Imidazolium Salts
197(5)
Preparation of Triazolium Salts
202(1)
Preparation of Imidazolinium Salts
203(2)
Preparation of Benzimidazolium Salts
205(1)
Application in Asymmetric Catalysis
205(23)
Palladium N-heterocyclic Carbene Complexes
205(5)
Rhodium N-heterocyclic Carbene Complexes
210(5)
Ruthenium N-heterocyclic Carbene Complexes
215(5)
Iridium N-heterocyclic Carbene Complexes
220(3)
Copper N-heterocyclic Carbene Complexes
223(5)
Isolated Complexes Without Application in Asymmetric Catalysis
228(1)
Conclusion
228(3)
References
228(3)
Chiral Ureas and Thiroureas in Asymmetric Catalysis
231(40)
J. A. J. Breuzard
M. L. Christ-Tommasino
M. Lemaire
Introduction
232(1)
Synthesis of Chiral Ureas and Thioures
233(5)
Symmetrical Ureas and Thioureas
234(1)
Symmetrical Diureas and Dithioureas
234(1)
Dissymetrical Ureas and Thioueas
234(2)
Amino-ureas and Amino-thioureas
236(1)
Polyureas and Polythioureas
236(2)
Coordination Chemistry
238(4)
Urea Coordination Modes to Transition Metals
238(1)
Thiourea Coordination Modes to Transition Metals
239(3)
Catalytic Activity of Urea- and Thiourea-Containing Complexes
242(12)
Asymmetric Reduction
242(1)
Hydrogen Transfer Reduction of C = O Bonds
242(4)
Hydrogenation of C = O and C = C Bonds
246(1)
Hydrosilylation
247(1)
Oxidation and Reaction with Epoxides
247(1)
Formation of C-C Bonds
248(1)
Reactions Involving CO
249(1)
Hydroformylation
249(2)
Alkoxycarbonylation
251(2)
Bismethoxycarbonylation
253(1)
Organocatalysis: Ureas and Thioureas as Organic Catalysts
254(11)
Strecker Reaction: CN Addition
255(1)
Asymmetric Strecker Synthesis
255(1)
Solid Phase Synthesis for High Throughput Screening
256(1)
Homogeneous Strecker Synthesis
257(1)
Recent Developments: Urea vs. Thiourea Ligands
257(1)
Structural Characteristics and Reaction Mechanism
258(1)
Other Substrates
258(1)
Industrial Applications
259(1)
Nitrone Cyanation
259(1)
Mannich Reactions
259(1)
Phosphorylation
260(1)
Michael Reactions
261(1)
Aza-Henry and Nitroaldol Reactions
262(1)
Diels-Alder Reactions
263(1)
Thioureas as Chiral Bases
264(1)
Conclusion
265(6)
References
266(5)
Chiral-at-Metal Complexes as Asymmetric Catalysts
271(18)
M. Fontecave
O. Hamelin
S. Menage
Introduction
271(1)
Chirality at Metal Centers
272(2)
Preparation of Chiral-at-Metal Complexes
274(9)
Resolution Methods
274(3)
Stereoselective Synthesis
277(1)
Induction by a Chiral Ligand
278(3)
Induction by Chiral Ions
281(1)
Asymmetric Transformation
282(1)
Enantioselective Catalysis with Chiral-at-Metal Complexes
283(6)
References
287(2)
Author Index Volumes 1--15 289(8)
Subject Index 297

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