More Synthetic Approaches to Nonaromatic Nitrogen Heterocycles, 2 Volume Set

Ana Maria M.M. Faisca Phillips, PhD, is Researcher at the Coordination Chemistry and Catalysis Group, Centro de Química Estrutural, Instituto Superior Técnico Universidade de Lisboa.

List of Contributors

Preface

List of Common Abbreviations

 

PART 1: CASCADE REACTIONS

 

1             Unity is Strength: The Case of Cascade Reactions Combined with C–H Activation  1

               Emanuele  Casali, Ervis Saraci and Giuseppe Zanoni

              

1.1         Introduction

1.2         Rhodium Promoted Reactions

1.3         Palladium Promoted Reactions

1.4         Ruthenium Promoted Reactions

1.5         Cobalt Promoted Reactions

1.6         Miscellaneous

References

 

2             Chemo-enzymatic Cascade Reactions for the Synthesis of Chiral Intermediates

               and Nonaromatic Nitrogen Heterocycles

Rodrigo O.M.A. de Souza, Raquel A.C. Leão, Marcelo A. Nascimento, Alexandre de S. França, Amanda S. de Miranda, Ivaldo I. Junior

 

2.1         Introduction

2.2         C–N Bond Construction Enzymes

2.3         C–N Deracemization Enzymes

2.4         Cascade Reactions

2.4.1      Enzymatic Cascade Reactions

2.4.2      Chemoenzymatic Cascade Reactions

References

 

3             Asymmetric Organocatalytic Cascade Reactions for the Synthesis of Nitrogen Heterocycles

A. M. M. M. Faisca Phillips

 

3.1 Introduction

3.2 Three-membered Ring Heterocycles: Aziridines

3.3 Four-membered Ring Heterocycles: The β-lactams

3.4 Five-membered Rings

3.4.1 Pyrrolidines

3.4.2 Pyrrolidinones (-Lactams)

3.4.3 Isoindolinones and Spirooxindoles

3.5 Six-membered Rings

3.5.1 Piperidines, Dihydropyridines and Tetrahydropyridines

3.5.2 Piperidinones (-lactams)

3.5.3 Dihydropyridinones

3.5.4 Tetrahydroquinolines, Dihydroquinolines and Related Substances

3.5.5 Hexahydropyridazines and Pyrimidinones

3.6 Pyrrolo[3,2,1-ij]quinolines

3.7 Cyclic Sulfamidates

3.8 Miscellaneous

Conclusion

References

 

 

PART 2: SELECTED REACTIONS FOR THE SYNTHESIS OF NITROGEN HETEROCYCLES

 

4             Synthesis of Nitrogen-Heterocycles Based on N-Heterocyclic Carbene Organocatalysis

               Hideto Miyabe

              

 

4.1         Introduction

4.2         NHC-catalyzed Cyclization

4.3         NHC-catalyzed Annulation

4.3.1      [3 + 2] Annulation

4.3.2      [4 + 2] Annulation

4.3.3      [3 + 3] Annulation

4.3.4      [4 + 3] Annulation

4.3.5      [2 + 2] Annulation

4.4         Oxidative NHC-catalyzed Annulation

4.4.1      Oxidative [3 + 2] Annulation

4.4.2      Oxidative [4 + 2] Annulation

4.4.3      Oxidative [3 + 3] Annulation

4.4.4      Oxidative [4 + 3] Annulation

4.4.5      Oxidative [2 + 2] Annulation

4.5         Asymmetric Dearomatization

4.6         Cooperative Catalysis of NHC and Transition-Metal Catalysts

4.7         Other NHC-catalyzed Reactions

4.8         Conclusion and Outlook

References

 

5             Synthesis of N-Heterocycles via [3 + n] Cycloaddition Reactions of Vinyl Metal Carbene Intermediates

               Ming Bao, Su Zhou, and Xinfang Xu

              

 

5.1         Introduction

5.2         [3 + 1]-Cycloaddition

5.3         [3 + 2]-Cycloaddition

5.4         [3 + 3]-Cycloaddition

5.4.1      [3 + 3]-Cycloaddition with Nitrone

5.4.2      [3 + 3]-Cycloaddition with Azomethine Imines

5.4.3      [3 + 3]-Cycloaddition with Other 1,3-Dipoles

5.5         [3 + 4]-Cycloaddition

5.5.1      [3 + 4]-Cycloaddition with N-Heterocycles

5.5.2      [3 + 4]-Cycloaddition with α,-Unsaturated Imines

5.5.        Other Types of [3 + 4]-Cycloadditions

5.6         [3 + 5]-Cycloaddition

5.7         Intramolecular Cyclization via Carbene/Alkyne Metathesis Process

5.8         Summary and Outlook

References

 

6             Recent Progress in the Synthesis of Amine-containing Heterocycles by Metathesis Reactions

               Zeyue Zhang, Damien Hazelard, and Philippe Compain

              

 

6.1         Introduction

6.2         Five-membered Cyclic Amines

6.3         Six-membered Cyclic Amines

6.3.1      Natural Products and Related Compounds

6.3.2      Sugar Mimetics

6.3.3      RCM of Phenylamines and Related Analogues

6.3.4      Miscellaneous

6.4         Seven-membered to Macrocyclic Amines

6.5         Tandem Reactions

6.6         Conclusion

References

 

7             Metal-Catalyzed Synthesis of N-Heterocycles Via Borrowing-Hydrogen Annulation

               A. Sofia Santos, Daniel Raydan, Nuno Viduedo, M. Manuel B. Marques, and Beatriz Royo

 

7.1         Introduction

7.2         Metal-Catalyzed Borrowing Hydrogen Annulation Reactions

7.2.1      Rh-Catalyzed Borrowing Hydrogen Reactions

7.2.2      Ru-Catalyzed Borrowing Hydrogen Reactions

7.2.3      Ir-Catalyzed Borrowing Hydrogen Reactions

7.2.4      Fe-Catalyzed Borrowing Hydrogen Reactions

7.2.5      Ni-Catalyzed Borrowing Hydrogen Reactions

7.3         Conclusions

References

 

8             Synthesis of N-Heterocycles Via Metal-Catalyzed Intramolecular Buchwald-Hartwig C-N Cross Coupling Reactions

               Auxiliadora Prieto

 

8.1         Introduction

8.2.        Applications of Intramolecular Pd-Catalyzed N-Arylation of amine in the Synthesis of Nonaromatic Heterocycles.

8.2.1.     Synthesis of Five-membered N-Heterocycles.

8.2.2.     Synthesis of Six-membered N-Heterocycles.

8.2.3.     Applications in the Synthesis of both Five- and Six-membered N-Heterocycles

8.2.4.     Synthesis of Seven-membered N-Heterocycles

8.3.        Applications of Intramolecular Pd-Catalyzed N-arylation of amide in the Synthesis of Nonaromatic Heterocycles.

8.3.1.     Applications in the Synthesis of Five-membered N-Heterocycles.

8.3.2.     Application in the Synthesis of Six-membered N-Heterocycles

8.3.3.     Application in the Synthesis of Seven-membered N-Heterocycles

8.4.        Intramolecular Pd-Catalyzed Arylation of Sulfonamides.

8.5         Applications of the Intramolecular Buchwald-Hartwig Amination in the Synthesis of Natural Products.

8.6         Conclusion

References

 

9             Synthesis of Nonaromatic Nitrogen Heterocycles Via Singlet Oxygen

               João Tomé, Kelly A.D.F. Castro, Leandro M. O. Lourenço, Roberto Santana Da Silva,

              

 

9.1         Introduction

9.2         Singlet Oxygen on Organic Synthesis

9.2.1      Oxidation of Bipyrroles

9.2.2      Synthesis of (R)-methylnaltrexone

9.2.3      Synthesis of Glochidine and Glochidicine

9.2.4      Synthesis of γ-lactams via One-pot Synthesis

9.2.5      Synthesis of the Melohenine B

9.2.6      Synthesis of Pyrrolidine Derivatives by [2 + 3] Cycloaddition, via 1O2 Mediated 1,3-dipole

9.2.7      Synthesis of Pandamarine

9.2.8      Preparation of Bicyclic Lactam

9.2.9      Synthesis of Alkaloids

9.2.10   Synthesis of Azaspiro Frameworks

9.2.11 Preparation of Tetrahydropyranopyrrolones

9.2.12 Synthesis of 2-oxindoles

9.2.13 Synthesis of Several Natural Products from an Amino Furan Derivative

9.2.14 Synthesis of Peptide-fluorescent Probes

9.2.15 Synthesis of Tetrahydroquinoline

9.3         Conclusion

References

 

10           Cobalt-catalysed Carbonylation for the Synthesis of N-Heterocyclic Compounds

               Anup Paul and Armando J.L. Pombeiro

              

 

1.            Introduction

2.            Cobalt-catalysed Carbonylation for the Synthesis of N-heterocyclic Compounds Using CO Gas as CO source

3.            Cobalt-catalysed Carbonylation for the Snthesis of N-heterocycles Using CO Surrogates

4.            Conclusions

References

 

11           Enantioselective Synthesis of Nitrogen Heterocycles Using Chiral Hypervalent Iodine Reagents

               Ana Maria Faisca Phillips and Armando J.L. Pombeiro

 

11.1       Introduction

11.2       The Historical Development of Chiral Hypervalent Iodine Reagents

11.3       Synthesis with Chiral Hypervalent Iodine Reagents

11.3.1   Difunctionalization of Alkenes

11.3.2   Dearomatization Reactions

11.3.3   α-Functionalization of Carbonyl Compounds

11.4       Conclusion

References

 

PART III. SPECIAL TECHNIQUES

 

12           Continuous Flow Chemistry

               Marcus Baumann

              

 

12.1       Introduction To Modern Flow Chemistry

12.2       Value of Heterocyclic Chemistry for Modern Drug Discovery Programs

12.3       Case Studies of Flow Chemistry Applied to Heterocyclic Targets

12.3.1    Flow Synthesis of Three-membered Saturated Heterocycles

12.3.2    Flow Synthesis of Four-membered Saturated Heterocycles

12.3.3    Flow Synthesis of Five-membered Saturated Heterocycles

12.3.4    Flow Synthesis of Six-membered Saturated Heterocycles

12.3.5    Flow Synthesis of Seven-membered Saturated Heterocycles

12.3.6    Flow Synthesis of Macrocyclic Saturated Heterocycles

12.4       Assessment of the Merits of Continuous Flow Processing for Heterocycle Synthesis

12.5       Summary and Conclusions

References

 

13           The Electrochemical Synthesis of Non-Aromatic N-Heterocycles

Oana R. Luca

 

13.1       Introduction

13.2       Laws of Organic Electrosynthesis

13.2.1    Types of Electrolyses

13.2.2    Diagnostic Analytical Methods: Voltammetry

13.3.      Construction of Three- and Four Membered Non-Aromatic Heterocycles

13.3.1 Aziridines

13.3.2 Epoxides

13.3.3 Azetidines

13.4       Construction of Five Six and Seven Membered Non-Aromatic Heterocycles

13.4.1   Pyrrolidines

13.4.2   Indolines and dihydrobenzofurans

13.4.3   Pyrrolidinones, 5-membered Cyclic Carbamates and Derivatives

13.4.4   Tetrahydrooxazole and Tetrahydrooxazine Derivatives

13.4.5   6-membered Amides, Carbamates, and Derivatives

13.5       Construction of Nonaromatic Heterocycles with Fused Polycyclic Systems

13.5.1   Nonaromatic Heterocycles from Phtalimides and Succinimides

13.5.2   Polyciclic Peptides

13.5.3   Polyclic Ureas

13.5.5   Ring-fused Quinones

Conclusion

References

 

14          Asymmetric Organocatalysis in Alternative Media

               Luis C. Branco, Verônica Diniz, Karolina Zalewska, and Miguel M. Santos

              

 

14.1       Introduction

14.2       Water as Reaction Medium

14.3       Ionic Liquids as Alternative Media

14.4       Miscellaneous Alternative Reaction Media

14.5       Conclusions

References

 

PART IV. SYNTHETIC METHODS FOR SPECIAL COMPOUND CLASSES

 

15           The Strained Aziridinium Ion

               Jala Ranjith and Hyun-Joon Ha

              

 

15.1       Introduction

15.2       Formation of Aziridinium Ions

15.3       Ring Opening of Aziridinium Ion

15.4       Synthetic Applications

15.5       Bicyclic Aziridinium Ion and its Application

Ackowledgments

References

 

16           Recent advances on the synthesis of azepane-based compounds

               Maria Assunta Chiacchio, Laura Legnani, Ugo Chiacchio, and Daniela Iannazzo

 

16.1       Introduction

16.2       Azepane Synthesis

16.2.1    Synthesis of Substituted Azepanes

16.2.2 Synthesis of Ring-fused Azepanes

16.2.3 Synthesis of Azepane-based Alkaloids

Conclusion

 

 

 

 

 

 

 

 

17           1,4-Diazepane Ring-based Systems

               Eduarda M.P. Silva, Pedro A.M.M. Varandas, and Artur M.S. Silva

 

17.1       Introduction

17.2       Reductive Amination

17.3       Mitsunobu Amination

17.4       1,3-Dipolar Cycloaddition

17.5       Multicomponent Reactions

17.6       Other Methods

Conclusions

References

 

18           Transition Metal Promoted Synthesis of Isoindoline Derivatives

               Laura A. Aronica and Gianluigi Albano

 

18.1       Introduction

18.2       Synthesis of Isoindolines

18.2.1    [2+2+2] Cycloaddition Reactions

18.2.2    Transition Metal-promoted Diels-Alder reactions

18.2.3    Transition Metal-promoted Cyclization of Ortho-substituted Benzyl Amines (and Derivatives)

18.2.4    Transition Metal-promoted 5-exo-dig Cyclization by C-C Bond Formation

18.2.5    Miscellaneous

18.2.6    Conclusions and Perspectives

References

 

19          1,2-Benzisothiazole 1,1-Dioxide (Saccharinate)-Based Compounds: Synthesis, Reactivity and    Applications

               Luís M.T. Frija, André L. Fernandes, Bruno Guerreiro, and M. Lurdes S. Cristiano

 

19.1       Introduction

19.2       Synthesis of Saccharinate-based Conjugates

19.3       Applications

19.3.1    Ionic Liquids

19.3.2    Coordination Chemistry

19.3.3    Biological Activity and Medical Uses

19.4       Concluding Remarks

References

 

20          Fused Heterocycles

               Arruje Hameed, Muhammad Abdul Qayyum, Abdur Rehman, Touseef Ur Rehman, Anwar Ahmad, and Tahir Farooq

 

20.1       Introduction

20.1       Recent Developments for Facile Synthesis and Applications of 1,2,4-Triazole Fused Heterocycles

20.1.1    1,2,4-Triazole-fused Heterocycles as Energetic Materials

20.1.2    1,2,4-Triazole-fused Heterocycles as Building Blocks

20.2       Recent Developments for Facile Synthesis of 1,2,3-Triazole-fused Heterocycles

20.2.1    1,2,3-Triazole-fused Heterocycles as Bioactive Scaffolds

20.2.2    1,2,3-Triazole-fused Heterocycles as Functional Materials

20.3       Conclusion

References

 

 

21          Recent Advances in the Design and Synthesis of Cyclic Peptidomimetics

               Arruje Hameed, Amjad Hameed, Ghulam Hussain, Hafiz Abdul Qayyum, Muhammad Fayyaz Farid, and Tahir Farooq

 

21.1       Introduction

21.2       Click-mediated Approaches for Cyclic Peptidomimetics

21.3       Enzyme-mediated Approaches for Cyclic Peptidomimetics

21.4       Solid-phase Synthesis of Cyclic Peptidomimetics

21.5       Conclusion

References