Hydrogen Bonding in Organic Synthesis

by Pihko, Petri M.

• ISBN13: 9783527318957
• ISBN10: 352731895X
• Edition: 1st
• Format: Hardcover
• Copyright: 2009-11-23
• Publisher: Wiley-VCH

Summary

This first comprehensive overview of the rapidly growing field emphasizes the use of hydrogen bonding as a tool for organic synthesis, especially catalysis. As such, it covers such topics as enzyme chemistry, organocatalysis and total synthesis, all unified by the unique advantages of hydrogen bonding in the construction of complex molecules from simple precursors. Providing everything you need to know, this is a definite must for every synthetic chemist in academia and industry.

Author Biography

After a postdoctoral stay with K. C. Nicolaou, Petri Pihko joined the faculty of Helsinki University of Technology, where his group was awarded the "Outstanding Junior Research Group" award of the University in 2004. His current research interests include organocatalysis, catalyst design, and total synthesis.

Table of Contents

Preface	p. ix
List of Contributors	p. xi
Introduction	p. 1
Introduction	p. 1
Hydrogen Bonding in Organic Synthesis	p. 3
References	p. 4
Hydrogen-Bond Catalysis or Brønsted-Acid Catalysis? General Considerations	p. 5
Introduction	p. 5
What is the Hydrogen Bond?	p. 6
Hydrogen-Bond Catalysis or Brønsted-Acid Catalysis	p. 7
Brønsted-Acid Catalysis	p. 9
Hydrogen-Bond Catalysis	p. 11
References	p. 13
Computational Studies of Organocatalytic Processes Based on Hydrogen Bonding	p. 15
Introduction	p. 15
Catalytic Functions of Hydrogen Bonds	p. 18
Dynamic Kinetic Resolution (DKR) of Azlactones-Thioureas Can Act as Oxyanion Holes Comparable to Serine Hydrolases	p. 19
The Calculated Reaction Path of the Alcoholytic Ring Opening of Azlactones	p. 19
How Hydrogen Bonds Determine the Enantioselectivity of the Alcoholytic Azlactone Opening	p. 23
On the Bifunctionality of Chiral Thiourea-Tert-Amine-Based Organocatalysts: Competing Routes to C-C Bond Formation in a Michael Addition	p. 25
Dramatic Acceleration of Olefin Epoxidation in Fluorinated Alcohols: Activation of Hydrogen Peroxide by Multiple Hydrogen Bond Networks	p. 29
Hydrogen Bond Donor Features of HFIP	p. 30
The Catalytic Activity of HFIP in the Epoxidation Reaction	p. 30
TADDOL-Promoted Enantioselective Hetero-Diels-Alder Reaction of Danishefsky's Diene with Benzaldehyde-Another Example for Catalysis by Cooperative Hydrogen Bonding	p. 37
Epilog	p. 40
References	p. 41
Oxyanion Holes and Their Mimics	p. 43
Introduction	p. 43
What are Oxyanion Holes?	p. 44
Contributions of Oxyanion Holes to Catalysis	p. 44
Properties of Hydrogen Bonds of Oxyanion Holes	p. 47
A More Detailed Description of the Two Classes of Oxyanion Holes in Enzymes	p. 49
A Historical Perspective	p. 49
Oxyanion Holes with Tetrahedral Intermediates	p. 52
Oxyanion Holes with Enolate Intermediates	p. 56
Examples of Enolate Oxyanion Holes	p. 58
Oxyanion Hole Mimics	p. 61
Mimics of Enzymatic Oxyanion Holes and Similar Systems	p. 61
Utilization of Oxyanion Holes in Enzymes for Other Reactions	p. 64
Concluding Remarks	p. 67
Acknowledgments	p. 67
References	p. 67
Brønsted Acids, H-Bond Donors, and Combined Acid Systems in Asymmetric Catalysis	p. 73
Introduction	p. 73
Brønsted Acid (Phosphoric Acid and Derivatives)	p. 75
Binapdiylphosphoric Acids	p. 75
Mannich Reaction	p. 75
Hydrophosphonylation	p. 78
Friedel-Crafts	p. 79
Diels-Alder	p. 83
Miscellaneous Reactions	p. 85
Nonimine Electrophiles	p. 89
Transfer Hydrogenation	p. 89
Nonbinol-Based Phosphoric Acids	p. 91
N-Trifiyl Phosphoramide	p. 95
Asymmetric Counteranion-Directed Catalysis	p. 98
N-H Hydrogen Bond Catalysts	p. 99
Guanidine Organic Base	p. 99
Ammonium Salt Catalysis	p. 106
Chiral Tetraaminophosphonium Salt	p. 109
Combined Acid Catalysis	p. 109
Brønsted-Acid-Assisted Brønsted Acid Catalysis	p. 110
Diol Activation of Carbonyl Electrophiles	p. 111
Diol Activation of Other Electrophiles	p. 116
Miscellaneous BBA and Related Systems	p. 120
Lewis-Acid-Assisted Brønsted Acid Catalysis	p. 122
Brønsted-Acid-Assisted Lewis Acid Catalysis (Cationic Oxazaborolidine)	p. 126
Diels-Alder Reactions	p. 126
Miscellaneous Reactions	p. 132
References	p. 136
(Thio)urea Organocatalysts	p. 141
Introduction and Background	p. 141
Synthetic Applications of Hydrogen-Bonding (Thio)urea Organocatalysts	p. 149
Nonstereoselective (Thio)urea Organocatalysts	p. 149
Privileged Hydrogen-Bonding N, N'-bis-[3, 5-(Trifluoromethyl)phenyl]thiourea	p. 149
Miscellaneous Nonstereoselective (Thio)urea Organocatalysts	p. 174
Stereoselective (Thio)urea Organocatalysts	p. 185
(Thio)ureas Derived From Trans-l,2-Diaminocyclohexane and Related Chiral Primary Diamines	p. 185
(Thio)ureas Derived from Cinchona Alkaloids	p. 253
(Thio)urea Catalysts Derived from Chiral Amino Alcohols	p. 288
Binaphthyl-Based (Thio)urea Derivatives	p. 296
Guanidine-Based Thiourea Derivatives	p. 307
Saccharide-Based (Thio)urea Derivatives	p. 315
Miscellaneous Stereoselective (Thio)urea Derivatives	p. 324
Summary and Outlook	p. 330
Acknowledgment	p. 332
Abbreviations and Acronyms	p. 333
References	p. 336
Appendix: Structure Index	p. 345
Highlights of Hydrogen Bonding in Total Synthesis	p. 353
Introduction	p. 353
Intramolecular Hydrogen Bonding in Total Syntheses	p. 353
Thermodynamic Control of Stereochemistry	p. 353
Pinnatoxin A	p. 353
Azaspiracid-1	p. 355
Kinetic Control Stereochemistry	p. 355
Pancratistatin	p. 355
Tunicamycins	p. 357
Callystatin	p. 358
Resorcylides	p. 359
Strychnofoline	p. 361
Asialo GM1	p. 361
Activation/Deactivation of Reactions	p. 362
Rishirilide B	p. 362
2-Desoxystemodione	p. 363
Leucascandrolide A	p. 363
Azaspirene	p. 364
Intermolecular Hydrogen Bondings in Total Syntheses	p. 365
Henbest Epoxidation	p. 365
Epoxyquinols	p. 366
Epoxide-Opening Cascades	p. 367
Conclusions	p. 369
References	p. 369
Index	p. 373
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