Organic Reactions, Volume 99

 
Standards Information Network (Verlag)
  • 1. Auflage
  • |
  • erschienen am 13. Juni 2019
  • |
  • 704 Seiten
 
E-Book | ePUB mit Adobe-DRM | Systemvoraussetzungen
978-1-119-57041-7 (ISBN)
 
ORGANIC REACTION
1. Auflage
  • Englisch
  • USA
John Wiley & Sons Inc
  • Für Beruf und Forschung
  • 53,80 MB
978-1-119-57041-7 (9781119570417)

weitere Ausgaben werden ermittelt
SCOTT E. DENMARK is the R. C. Fuson Professor of Chemistry at the University of Illinois at Urbana-Champaign. In addition to his editor-in-chief role for Organic Reactions, he is an editor for Organic Syntheses and for the Encyclopedia of Reagents for Organic Synthesis, both available from Wiley.
1. Addition of Non-Stabilized Carbon-Based Nucleophilic Reagents to Chiral N-Sulfinyl Imines 1
Melissa A. Herbage, Jolaine Savoie, Joshua D. Sieber, Jean-Nicolas Desrosiers, Yongda Zhang, Maurice A. Marsini, Keith R. Fandrick, Daniel Rivalti, and Chris H. Senanayake

2. Iridium-Catalyzed, Enantioselective, Allylic Alkylations with Carbon Nucleophiles 423
Jian-Ping Qu, Gunter Helmchen, Ze-Peng Yang, Wei Zhang, and Shu-Li You

Cumulative Chapter Titles by Volume 633

Author Index, Volumes 1-99 651

Chapter and Topic Index, Volumes 1-99 657

Chapter 1
Addition of Non-Stabilized Carbon-Based Nucleophilic Reagents to Chiral N-sulfinyl Imines


Melissa A. Herbage Jolaine Savoie Joshua D. Sieber Jean-Nicolas Desrosiers Yongda Zhang Maurice A. Marsini Keith R. Fandrick Daniel Rivalti and Chris H. Senanayake

Boehringer Ingelheim Pharmaceuticals Inc., 900 Ridgebury Rd., Ridgefield, CT 06877, United States

Contents


  1. Introduction
  2. Mechanism and Stereochemistry
  3. Computational and Experimental Studies
  4. Stereochemical Models
  5. Effect of the Organometallic Reagent
  6. Effect of the Solvent
  7. Effects of Additives
  8. Effect of Coordinating Substituents at the a-Position
  9. Effect of a Stereogenic a-Carbon
  10. Scope and Limitations
  11. Preparation of N-Sulfinyl Imines
  12. Preparation of N-Sulfinyl Aldimines
  13. Preparation of N-Sulfinyl Ketimines
  14. Additions of Alkyl Nucleophiles to N-Sulfinyl Imines
  15. Additions of Alkyl Nucleophiles to N-Sulfinyl Aldimines
  16. Additions of Alkyl Nucleophiles to N-Sulfinyl Ketimines
  17. Additions of Alkenyl Nucleophiles to N-Sulfinyl Imines
  18. Additions of Alkenyl Nucleophiles to N-Sulfinyl Aldimines
  19. Addition of Alkenyl Nucleophiles to N-Sulfinyl Ketimines
  20. Additions of Aryl Nucleophiles to N-Sulfinyl Imines
  21. Additions of Aryl Nucleophiles to N-Sulfinyl Aldimines
  22. Additions of Aryl Nucleophiles to N-Sulfinyl Ketimines
  23. Additions of Allylic Nucleophiles to N-Sulfinyl Imines
  24. Additions of Allylic Nucleophiles to N-Sulfinyl Aldimines
  25. Additions of Allylic Nucleophiles to N-Sulfinyl Ketimines
  26. Additions of Propargylic Nucleophiles to N-Sulfinyl Imines
  27. Additions of Propargylic Nucleophiles to N-Sulfinyl Aldimines
  28. Additions of Propargylic Nucleophiles to N-Sulfinyl Ketimines
  29. Additions of Alkynyl Nucleophiles to N-Sulfinyl Imines
  30. Additions of Alkynyl Nucleophiles to N-Sulfinyl Aldimines
  31. Additions of Alkynyl Nucleophiles to N-Sulfinyl Ketimines
  32. Nucleophilic Additions of Cyanide to N-Sulfinyl Imines
  33. Nucleophilic Additions of Cyanide to N-Sulfinyl Aldimines
  34. Nucleophilic Additions of Cyanide to N-Sulfinyl Ketimines
  35. Removal and Recovery of the N-Sulfinyl Auxiliary
  36. Applications to Synthesis
  37. Synthesis of Amino Acids
  38. Synthesis of Active Pharmaceutical Ingredients
  39. Bradykinin B1 Antagonists
  40. ß-Secretase-1 (BACE) Inhibitors
  41. Plasmodium Dipeptidyl Aminopeptidase (DPAP) Inhibitors
  42. Cholesteryl Ester Transfer Protein (CETP) Inhibitors
  43. Kinase Inhibitors
  44. Melanocortin Type 4 Receptor (MC4R)
  45. Cetirizine
  46. Synthesis of Natural Products
  47. Tubulysins
  48. Polyoxins
  49. Syomycin A
  50. (-)-3-Demethoxyerythratidinone
  51. Comparison With Other Methods
  52. Chiral Auxiliaries
  53. Catalytic Enantioselective Methods
  54. Hydrogenation of Imines and Enamides
  55. Experimental Conditions
  56. General Considerations on Safety
  57. Handling Pyrophoric Reagents
  58. Handling Cyanide Reagents
  59. Experimental Procedures
  60. (R)-2-Methyl-N-((S)-1-phenylethyl)propane-2-sulfinamide [Addition of an Alkylmagnesium Nucleophile to an N-Sulfinyl Aldimine].5 ,36
  61. (R)-2-Methyl-N-((S)-2-phenylhexan-2-yl)propane-2-sulfinamide [Addition of an Alkylaluminum Nucleophile to an N-Sulfinyl Ketimine].36 ,88
  62. (R)-2-Methyl-N-((R)-1-phenylhex-2-en-1-yl)propane-2-sulfinamide [Addition of an Alkenylboron Nucleophile to an N-Sulfinyl Aldimine].43
  63. (S)-1-((R)-tert-Butylsulfinyl)-2-phenyl-2-(prop-1-en-2-yl)aziridine [Addition of an Alkenylmagnesium Nucleophile to an N-Sulfinyl Ketimine].187
  64. (R)-2-Methyl-N-((R)-1-phenylpropyl)propane-2-sulfinamide [Addition of an Arylmagnesium Nucleophile to an N-Sulfinyl Aldimine].36
  65. (R)-2-Methyl-N-((R)-2-methyl-3-phenylpentan-3-yl)propane-2-sulfinamide [Addition of an Arylaluminum Nucleophile to an N-Sulfinyl Ketimine].36
  66. (R)-2-Methyl-N-((S)-1-phenylbut-3-en-1-yl)propane-2-sulfinamide [Addition of an Allylindium Nucleophile to an N-Sulfinyl Aldimine].65
  67. (R)-2-Methyl-N-((R)-1-phenylbut-3-en-1-yl)propane-2-sulfinamide [Addition of an Allylzinc Nucleophile to an N-Sulfinyl Aldimine].65
  68. (R)-2-Methyl-N-((S)-2-(4-(trifluoromethyl)phenyl)pent-4-en-2-yl)propane-2-sulfinamide [Addition of an Allylindium Nucleophile to an N-Sulfinyl Ketimine].65
  69. (R)-2-Methyl-N-((S)-1-phenyl-4-(trimethylsilyl)but-3-yn-1-yl)propane-2-sulfinamide [Addition of a Propargylzinc Nucleophile to an N-Sulfinyl Aldimine].244
  70. (R)-2-Methyl-N-((R)-3-methyl-6-(trimethylsilyl)hex-5-yn-3-yl)propane-2-sulfinamide [Addition of a Propargylindium Nucleophile to an N-Sulfinyl Ketimine].246
  71. (R)-2-Methyl-N-((R)-1-phenyl-3-(trimethylsilyl)prop-2-yn-1-yl)propane-2-sulfinamide [Addition of an Alkynylmagnesium Nucleophile to an N-Sulfinyl Aldimine].200
  72. (S)-2-Methyl-N-((S)-2-((1R,4S)-4-methylcyclohexyl)-4-(trimethylsilyl)but-3-yn-2-yl)propane-2-sulfinamide [Addition of an Alkynylaluminum Nucleophile to an N-Sulfinyl Ketimine].250
  73. (S)-N-((S)-Cyano(phenyl)methyl)-4-methylbenzenesulfinamide [Nucleophilic Addition of Cyanide to an N-Sulfinyl Aldimine].259
  74. (R)-N-((R)-1-Cyano-1-phenylethyl)-2-methylpropane-2-sulfinamide [Nucleophilic Addition of Cyanide to an N-Sulfinyl Ketimine].264
  75. Tabular Survey
  76. References

Introduction


Chiral branched amines are an extremely important class of molecules that can be found in numerous natural products and marketed pharmaceuticals. Among several general strategies for the asymmetric synthesis of amines, one of the most successful is the addition of carbon-based nucleophiles to imine derivatives bearing a readily cleavable chiral auxiliary to bias the stereoselectivity in the desired direction.1-3 Sulfinamides are one of the most widely used subsets of chiral auxiliaries. The growing number of sulfinamide-based methods and their application to total synthesis, to drug discovery, and to drug development4 is attributed to a number of practical aspects related to this chemistry. A wide range of sulfinamides can be prepared via straightforward synthetic procedures.5-18 Additionally, enantiomerically pure 4-toluene- and tert-butanesulfinamides are commercially available at a reasonable cost. N-Sulfinyl aldimines and ketimines can be synthesized using mild reaction conditions, and the resulting imines are easily handled. The N-sulfinyl group both activates the imines for nucleophilic attack and is a powerful directing group, leading to high diastereomeric ratios and predictable asymmetric induction (Scheme 1). Cleavage of the N-sulfinyl group is achieved using mild acidic conditions. Because of the increasing popularity of sulfinamide chemistry, a number of excellent reviews have been published.19-27 This chapter provides an overview of sulfinamide chemistry through 2017, excluding the patent literature, in which a carbon-carbon bond is formed between the azomethine carbon and the...

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