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Early Main Group Metal Catalysis: Concepts and Reactions [Kõva köide]

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  • Formaat: Hardback, 400 pages, kõrgus x laius x paksus: 249x175x23 mm, kaal: 885 g
  • Ilmumisaeg: 05-Feb-2020
  • Kirjastus: Blackwell Verlag GmbH
  • ISBN-10: 3527344489
  • ISBN-13: 9783527344482
Teised raamatud teemal:
Early Main Group Metal Catalysis: Concepts and ReactionsSuurem pilt
  • Formaat: Hardback, 400 pages, kõrgus x laius x paksus: 249x175x23 mm, kaal: 885 g
  • Ilmumisaeg: 05-Feb-2020
  • Kirjastus: Blackwell Verlag GmbH
  • ISBN-10: 3527344489
  • ISBN-13: 9783527344482
Teised raamatud teemal:
Püsilink: https://www.kriso.ee/db/9783527344482.html
Märksõnad:
Early Main Group Metal Catalysis gives a comprehensive overview of catalytic reactions in the presence of group 1 and group 2 metals. Chapters are ordered to reaction type, contain educational elements and deal with concepts illustrated by examples that cover the main developments. After a short introduction on polar organometallic chemistry and synthesis of early main group metal complexes, a variety of catalytic reactions are described, e.g. polymerization of alkenes, hydroamination and phosphination reactions, hydrosilylation, hydroboration and hydrogenation catalysis, as well as enantioselective and Lewis-acid catalysis. The book addresses organic chemists and researchers in industry interested in the state-of-the-art and new possibilities of early main group metal catalysis as well as newcomers to the field. Written by a team of leaders in the field, it is a very welcome addition to the area of main group metal chemistry, and to the field of catalysis.
Preface xiii
1 Introduction to Early Main Group Organometallic Chemistry and Catalysis 1(30)
Sjoerd Harder
1.1 Introduction
1(1)
1.2 s-Block Organometallics
1(16)
1.2.1 Short History
1(1)
1.2.2 Synthesis of Group 1 Organometallics
2(2)
1.2.3 Synthesis of Group 2 Organometallics
4(4)
1.2.4 Bonding and Structures of s-Block Organometallics
8(5)
1.2.5 Dynamics of s-Block Organometallics in Solution
13(3)
1.2.6 Low-Valent s-Block Chemistry
16(1)
1.3 s-Block Organometallics in Catalysis
17(7)
1.3.1 Working Principles in Lewis Acid Catalysis
17(2)
1.3.2 Working Principles in s-Block Organometallic Catalysis
19(2)
1.3.3 Substrate Activation by s-Block Metals
21(2)
1.3.4 Future of Early Main Group Metal Catalysis
23(1)
List of Abbreviations
24(1)
References
24(7)
2 Polymerization of Alkenes and Polar Monomers by Early Main Group Metal Complexes 31(28)
Sjoerd Harder
2.1 Introduction
31(1)
2.2 Alkene Polymerization
32(13)
2.2.1 Styrene Polymerization
33(7)
2.2.2 Polymerization of Modified Styrene
40(3)
2.2.3 Polymerization of Butadiene or Isoprene
43(2)
2.3 Polymerization of Polar Monomers
45(8)
2.3.1 Polymerization of Lactides
45(5)
2.3.2 Copolymerization of Epoxides and CO2
50(3)
2.4 Conclusions
53(1)
List of Abbreviations
54(1)
References
54(5)
3 Intramolecular Hydroamination of Alkenes 59(34)
Sebastian Bestgen
Peter W. Roesky
3.1 Introduction
59(1)
3.2 Hydroamination
60(4)
3.2.1 Scope
62(2)
3.3 s-Block Metal Catalysis
64(22)
3.3.1 General Remarks
64(1)
3.3.2 Mechanistic Aspects
65(3)
3.3.3 Group 1-Based Catalysis
68(6)
3.3.3.1 Concerted Reaction
68(3)
3.3.3.2 Radical-Mediated Intramolecular Hydroamination
71(1)
3.3.3.3 Reactions of N-Arylhydrazones and Ketoximes
72(2)
3.3.4 Group 2 Metal-Mediated Catalysis
74(9)
3.3.5 Group 2-Mediated Asymmetric Cyclohydroamination
83(1)
3.3.6 Lewis Acidic Metal Cation Catalysis
84(1)
3.3.7 Miscellaneous
85(1)
3.4 Outlook
86(1)
Acknowledgments
87(1)
List of Abbreviations
87(1)
References
88(5)
4 Molecular s-Block Catalysts for Alkene Hydrophosphination and Related Reactions 93(30)
Yann Sarazin
Jean-Francois Carpentier
4.1 Introduction
93(2)
4.2 General Considerations
95(1)
4.3 Hydrophosphination of Alkenes
96(16)
4.3.1 Precatalysts with Nitrogen-Based Ligands
97(13)
4.3.2 Precatalysts with Oxygen-Based Ligands
110(2)
4.4 Hydrophosphination of Carbodiimides
112(2)
4.5 Miscellaneous Reactions
114(3)
4.5.1 Hydrophosphinylation of Alkenes and Enones
114(2)
4.5.2 Hydrophosphonylation of Aldehydes and Ketones
116(1)
4.6 Summary and Conclusions
117(1)
List of Abbreviations
118(1)
References
118(5)
5 H-N and H-P Bond Addition to Alkynes and Heterocumulenes 123(28)
Sven Krieck
Matthias Westerhausen
5.1 Introduction
123(1)
5.2 Hydroamination
124(10)
5.2.1 Hydroamination with Secondary Amines
125(3)
5.2.2 Hydroamination with Primary Amines
128(2)
5.2.3 Proposed Mechanisms for the Hydroamination of Butadiynes
130(4)
5.3 Hydrophosphanylation (Hydrophosphination)
134(4)
5.4 Hydrophosphorylation and Hydrophosphonylation
138(5)
5.5 Summary and Conclusions
143(3)
5.6 Acknowledgments
146(1)
5.7 Abbreviations
146(1)
References
146(5)
6 Early Main Group Metal-Catalyzed Hydrosilylation of Unsaturated Bonds 151(24)
Sjoerd Harder
6.1 Introduction
151(1)
6.2 Historical Development
151(2)
6.3 Nonprecious Metal Hydrosilylation Catalysts
153(2)
6.4 C=C Bond Hydrosilylation with s-Block Metal Catalysts
155(6)
6.5 C=O Bond Hydrosilylation with s-Block Metal Catalysts
161(6)
6.6 C=N Bond Hydrosilylation with s-Block Metal Catalysts
167(3)
6.7 Conclusions
170(1)
References
171(4)
7 Early Main Group Metal Catalyzed Hydrogenation 175(26)
Heiko Bauer
Sjoerd Harder
7.1 Introduction
175(3)
7.2 Hydrogenation of C=C Double Bonds
178(9)
7.3 Hydrogenation of C=N Double Bonds
187(4)
7.4 Hydrogenation of C=O Double Bonds
191(3)
7.5 Summary and Perspectives
194(3)
References
197(4)
8 Alkali and Alkaline Earth Element-Catalyzed Hydroboration Reactions 201(24)
Aaron D. Sadow
8.1 Introduction and Overview
201(2)
8.2 Thermodynamic Considerations
203(4)
8.2.1 Hydroboration, Hydrosilylation, and Hydrogenation
203(2)
8.2.2 Thermochemistry of Metal-Oxygen Bonds and Element-Hydrogen Bonds
205(2)
8.3 Group 1-Catalyzed Hydroboration Reactions
207(7)
8.3.1 Overview
207(1)
8.3.2 Base-Catalyzed Hydroborations
207(3)
8.3.3 Alkali Metal Hydridoborate and Aluminate-Catalyzed Hydroboration
210(4)
8.4 Group 2-Catalyzed Hydroboration Reactions
214(8)
8.4.1 Overview
214(1)
8.4.2 β-Diketiminate Magnesium-Catalyzed Hydroborations
215(2)
8.4.3 Tris(4,4-dimethyl-2-oxazolinyl)phenylborato Magnesium-Catalyzed Hydroboration of Ester and Amides
217(4)
8.4.4 Magnesium Triphenylborate-Catalyzed Hydroboration
221(1)
8.4.5 Supported Catalysts for Hydroboration
221(1)
8.5 Summary and Conclusions
222(1)
References
222(3)
9 Dehydrocoupling and Other Cross-couplings 225(26)
Merle Arrowsmith
9.1 Introduction
225(3)
9.2 Early Main Group-Catalyzed Cross-DHC of Amines and Boranes
228(10)
9.2.1 Early Stoichiometric Studies with s-Block Elements
228(1)
9.2.2 s-Block-Catalyzed Cross-dehydrogenative Synthesis of Diaminoboranes
229(2)
9.2.3 s-Block-Catalyzed DHC of DMAB
231(4)
9.2.4 Calcium-Catalyzed Dehydrocoupling of tert-Butylamine Borane
235(1)
9.2.5 s-Block-Catalyzed DHC of Amines and Monohydroboranes
235(3)
9.3 s-Block-Catalyzed Cross-DHC of Amines and Silanes
238(5)
9.3.1 Influence of Precatalysts and Substrates on Reactivity and Selectivity
238(2)
9.3.2 Mechanistic and Computational Analysis
240(2)
9.3.3 Application to the Synthesis of Oligo- and Polysilazanes
242(1)
9.4 Other s-Block-Catalyzed Cross-DHC Reactions
243(1)
9.4.1 Alkali Metal-Catalyzed DHC of Si-H and O-H Bonds
243(1)
9.4.2 s-Block-Catalyzed DHC of Si-H and C-H Bonds
243(1)
9.5 Early Main Group-Mediated Nondehydrogenative Cross-couplings
244(1)
9.6 Conclusion and Outlook
245(1)
References
246(5)
10 Enantioselective Catalysis with s-Block Organometallics 251(28)
Philipp Stegner
Sjoerd Harder
10.1 Introduction
251(1)
10.2 Lithium-Based Catalysts
252(7)
10.2.1 Lithium Catalysts Based on Neutral Chiral Ligands
252(3)
10.2.2 Lithium Catalysts Based on Monoanionic Chiral Ligands
255(2)
10.2.3 Lithium Catalysts Based on Dianionic Chiral Ligands
257(2)
10.3 Potassium-Based Catalysts
259(3)
10.3.1 Potassium Catalysts Based on Monoanionic Chiral Ligands
260(2)
10.4 Magnesium-Based Catalysts
262(7)
10.4.1 Magnesium Catalysts Based on Monoanionic Chiral Ligands
263(3)
10.4.2 Magnesium Catalysts Based on Dianionic Chiral Ligands
266(3)
10.5 Calcium-Based Catalysts
269(6)
10.5.1 Calcium Catalysts Based on Monoanionic Chiral Ligands
269(4)
10.5.2 Calcium Catalysts Based on Dianionic Chiral Ligands
273(2)
10.6 Conclusion and Outlook
275(1)
List of Abbreviations
275(1)
References
276(3)
11 Early Main Group Metal Lewis Acid Catalysis 279(32)
Marian Rouser
Sebastian Schroder
Meike Niggemann
11.1 Introduction
279(8)
11.1.1 Lewis Acidity of s-Block Metal Cations
280(1)
11.1.2 Interactions with More than One Lewis Base
281(1)
11.1.3 Counter Anions
282(1)
11.1.4 Solvation
283(1)
11.1.5 Solubility and Aggregation
283(1)
11.1.6 Water Tolerance
284(1)
11.1.7 Relative Lewis Acid Activity of Alkaline and Alkaline Earth Metals
285(2)
11.1.8 Hidden Bronsted Acid
287(1)
11.2 Polarized Carbon-Heteroatom Double Bonds
287(9)
11.2.1 Carboxylates: Anhydrides and Carbonates
288(1)
11.2.2 Aldehydes, Ketones, and Formates
289(2)
11.2.3 α,β-Unsaturated Carbonyl Compounds
291(1)
11.2.4 Imines and Enamines
292(2)
11.2.5 Mannich Reactions
294(1)
11.2.6 Oxidation and Reduction
294(1)
11.2.7 Donor-Acceptor Cyclopropanes
294(1)
11.2.8 Diels-Alder Reaction and Cycloaddition
295(1)
11.3 Activation of Polarized Single Bonds
296(9)
11.3.1 Opening of Three-Membered Heterocycles
296(1)
11.3.2 Leaving Groups
297(2)
11.3.3 Ca2+-Catalyzed Dehydroxylation as a Special Case
299(6)
11.4 Activation of Unpolarized Double Bonds
305(2)
11.5 Summary and Conclusions
307(1)
References
307(4)
12 Enantioselective Group 2 Metal Lewis Acid Catalysis 311(36)
Yasuhiro Yamashita
Tetsu Tsubogo
Shu Kobayashi
12.1 Introduction
311(2)
12.2 Catalytic Enantioselective Reactions Using Chiral Magnesium Complexes
313(11)
12.2.1 Chiral Magnesium-Catalyzed Diels-Alder and 1,3-Dipolar Cycloaddition Reactions
313(2)
12.2.2 Chiral Magnesium-Catalyzed 1,4-Addition Reactions
315(3)
12.2.3 Chiral Magnesium-Catalyzed Addition Reactions to Carbonyl Compounds
318(1)
12.2.4 Chiral Magnesium-Catalyzed Addition Reactions with Imines
319(2)
12.2.5 Chiral Magnesium-Catalyzed Ring-Opening Reactions of Epoxide and Aziridine
321(2)
12.2.6 Chiral Magnesium-Catalyzed a-Functionalization Reactions of Carbonyl Compounds
323(1)
12.2.7 Various Chiral Magnesium-Catalyzed Reactions
324(1)
12.3 Catalytic Enantioselective Reactions Using Chiral Calcium Complexes
324(13)
12.3.1 Chiral Calcium-Catalyzed Addition Reactions to Carbonyl Compounds
324(2)
12.3.2 Chiral Calcium-Catalyzed 1,4-Addition Reactions
326(5)
12.3.3 Chiral Calcium-Catalyzed Addition Reactions with Imines
331(2)
12.3.4 Chiral Calcium-Catalyzed a-Functionalization Reactions with Carbonyl Compounds
333(1)
12.3.5 Chiral Calcium-Catalyzed Cycloaddition Reactions
334(1)
12.3.6 Chiral Calcium-Catalyzed Hydroamination Reactions
334(2)
12.3.7 Chiral Calcium-Catalyzed Epoxidation Reactions
336(1)
12.3.8 Chiral Calcium-Catalyzed Aziridine Ring-Opening Reaction
337(1)
12.4 Catalytic Enantioselective Reactions Using Chiral Strontium Complexes
337(2)
12.4.1 Chiral Strontium-Catalyzed 1,4-Addition Reactions
337(1)
12.4.2 Chiral Strontium-Catalyzed Addition Reactions with Imines
338(1)
12.4.3 Chiral Strontium-Catalyzed Oxime Formation
339(1)
12.5 Catalytic Enantioselective Reactions Using Chiral Barium Complexes
339(2)
12.5.1 Chiral Barium-Catalyzed Addition Reactions to Carbonyl Compounds and Imines
339(1)
12.5.2 Chiral Barium-Catalyzed 1,4-Addition Reactions
340(1)
12.5.3 Chiral Barium-Catalyzed Diels-Alder Reactions
341(1)
12.6 Summary and Outlook
341(1)
References
342(5)
13 Miscellaneous Reactions 347
Michael S. Hill
13.1 Introduction
347(1)
13.2 Privileged Substrates and s-Block Reactivity
347(4)
13.3 Reactivity with Multiply Bonded Substrates
351(10)
13.3.1 Tishchenko Dimerization of Aldehydes
351(1)
13.3.2 Trimerization of Organic Isocyanates
352(1)
13.3.3 Hydroalkoxylation of Alkynyl Alcohols
353(1)
13.3.4 Catalytic Isomerization and C-C Coupling with Terminal Alkynes
354(4)
13.3.5 Activation and Deoxygenation of C-O Multiple Bonds
358(3)
13.4 Single-Electron Transfer Steps in s-Block-Centered Catalysis
361(2)
13.5 "Beyond" Hydrofunctionalization and Dehydrocoupling
363(2)
13.6 Conclusions and Conjecture
365(2)
References
367
Index 37
Sjoerd Harder holds the Chair of Inorganic and Organometallic Chemistry at the University of Erlangen-Nuremberg, Germany. He has authored over 175 scientific publications, mainly on the topic of early main group metal chemistry and is considered a pioneer in heavier alkaline-earth metal chemistry and group 2 metal applications in catalysis.