Trienamines: Their Key Role in Extended Organocatalysis
for Diels-Alder Reactions

• Authors: Silvia Reboredo , Alejandro Parra , José Alemán
• Languages of publication: EN

Abstracts

EN

Activation via trienamine intermediates is a synthetically useful protocol for
performing asymmetric Diels-Alder reactions controlled by a remote chiral
catalyst (a secondary or primary amine). Key features underpinning this
concept are the conformation towards the trienamine formation and also
the use of highly electrophilic dienophiles. This cycloaddition reaction allows
the application of asymmetric organocatalysis at a remote position, and the
synthesis of complex molecules short synthetic sequences is possible.

Keywords

EN

Trienamine; Organocatalysis; Asymmetric catalysis; Diels-Alder reaction; Tandem reaction

• Publisher: De Gruyter Open
• Journal: Asymmetric Catalysis
• Year: 2013
• Volume: 1
• Issue: 1

Dates

received

14 - 3 - 2013

online

31 - 5 - 2013

accepted

6 - 4 - 2013

Contributors

author

Silvia Reboredo

• Departamento de Química Orgánica I,
  Facultad de Químicas, Universidad
  Complutense de Madrid

author

Alejandro Parra

• Departamento de Química Orgánica
  (Módulo 1), Facultad de Ciencias,
  Universidad Autónoma de Madrid
  Cantoblanco, 28049-Madrid

author

José Alemán

• Departamento de Química Orgánica
  (Módulo 1), Facultad de Ciencias,
  Universidad Autónoma de Madrid
  Cantoblanco, 28049-Madrid

References

• For some selected reviews in organocatalysis, see: a)Berkessel A., Göger H., Asymmetric Organocatalysis,WILEY-VCH, Weinheim, Germany, 2005. b) Dalko P. I.,Enantioselective Organocatalysis, WILEY-VCH, Weinheim,2007. c) Dalko P. I., Enantioselective Organocatalysis, Wiley-VCH, Weinheim, 2007. d) MacMillan D. W. C., The Adventand Development of Organocatalysis, Nature, 2008, 455,304-308. e) Moyano A., Rios R., Asymmetric OrganocatalyticCyclization and Cycloaddition Reactions, Chem. Rev. 2011,111, 4703-4832. f) Bernardi L., Fochi M., Franchini M. C.,Ricci A., Bioinspired Organocatalytic Asymmetric Reactions,Org. Biomol. Chem. 2012, 10, 2911-2922. g) Cabrera S., Alemán J., Applications of Asymmetric Organocatalysis inMedicinal Chemistry, Chem. Soc. Rev. 2013, 42, 774-793.
• For a seminal work in HOMO activation via enamineintermediates, see: a) List B., Lerner R. A., Barbas III C. F. J.,Proline-Catalyzed Direct Asymmetric Aldol Reactions, J. Am.Chem. Soc., 2000, 122, 2395-2396. For a review in enamineactivation, see: b) Mukherjee S., Yang J. W., Hoffmann S.,List B., Asymmetric Enamine Catalysis, Chem. Rev. 2007,107, 5471-5569. For a seminal work in HOMO-activation viadienamine intermediates, see: c) Bertelsen S., Marigo M.,Brandes S., Dinér P., Jørgensen K. A., Dienamine Catalysis:Organocatalytic Asymmetric γ-Amination of α,β-UnsaturatedAldehydes, J. Am. Chem. Soc. 2006, 128, 12973-12980.For reviews in dienamine activation, see: d) Ramachary D. B.,Reddy Y. V., Dienamine Catalysis: An Emerging Technologyin Organic Synthesis, Eur. J. Org. Chem., 2012, 865-887. e)Parra A., Reboredo S., Alemán J., Asymmetric Synthesis ofCyclobutanes by a Formal [2+2] Cycloaddition Controlled byDienamine Catalysis, Angew. Chem. Int. Ed. 2012, 51, 9734-9735.
• For a seminal work in LUMO activation, see: a) Ahrendt K. A.,Borths C. J., MacMillan D. W. C., New Strategies for OrganicCatalysis: The First Highly Enantioselective OrganocatalyticDiels−Alder Reaction, J. Am. Chem. Soc. 2000, 122, 4243-4244. For a review in LUMO activation, see: b) Erkkilä A.,Majander I., Pihko P. M., Iminium Catalysis, Chem. Rev.2007, 107, 5416-5470.
• For a seminal work in SOMO activation, see: a) Beeson T.D., Mastracchio A., Hong J., Ashton K., MacMillan D. W. C.,Enantioselective Organocatalysis Using SOMO Activation,Science 2007, 316, 582-585. For selected examples, see:b) Kim H., MacMillan D. W. C., Enantioselective Organo-SOMO Catalysis: The α-Vinylation of Aldehydes, J. Am.Chem. Soc. 2008, 130, 398-399. c) Rendler S., MacMillanD. W. C., Enantioselective Polyene Cyclization via Organo-SOMO Catalysis, J. Am. Chem. Soc. 2010, 132, 5027-5029.d) Jui N.T., Lee E. C., MacMillan D. W. C., EnantioselectiveOrgano-SOMO Cascade Cycloadditions: A Rapid Approachto Molecular Complexity from Simple Aldehydes and Olefins,J. Am. Chem. Soc. 2010, 132, 10015-10017. e) Devery J J.,Conrad J. C., MacMillan D. W. C., Flowers R. A., MechanisticComplexity in Organo–SOMO Activation, Angew. Chem., Int.Ed. 2010, 49, 6106-6110.
• For a review, see: a) Mikami K., Shimizu M., Zhang H.–C.,Maryanoff B. E., Acyclic Stereocontrol between RemoteAtom Centers via Intramolecular and Intermolecular Stereocommunication,Tetrahedron 2001, 57, 2917-2951. Forselected examples, see: b) Linnane P., Magnus N., MagnusP., Induction of Molecular Asymmetry by a Remote ChiralGroup, Nature 1997, 385, 799-801. c) Clayden A., LundL., Vallverdú L., Helliwell M., Ultra-remote Stereocontrolby Conformational Communication of Information along aCarbon Chain, Nature 2004, 431, 966-971.
• For recent reviews concerning trienamine, see: a) Arceo E.,Melchiorre P., Extending the Aminocatalytic HOMO-Raising Activation Strategy: Where Is the Limit?, Angew. Chem., Int.Ed. 2012, 51, 5290-5292. b) Kumar I., Ramaraju P., Mir N.A., Asymmetric Trienamine Catalysis: New Opportunities inAmine Catalysis, Org. Biomol. Chem. 2013, 11, 709-716.
• Jia Z.-J., Jiang H., Li J.-L., Gschwend B., Li Q.-Z., Yin X.,Grouleff J., Chen Y.-C., Jørgensen K. A., Trienamines inAsymmetric Organocatalysis: Diels−Alder and TandemReactions, J. Am. Chem. Soc. 2011, 133, 5053-5061.
• a) Lin H., Danishefsky S. J., Gelsemine: A Thought-Provoking Target for Total Synthesis, Angew. Chem.,Int. Ed. 2003, 42, 36–51. b) Galliford C. V., Scheidt K. A.,Pyrrolidinyl-Spirooxindole Natural Products as Inspirationsfor the Development of Potential Therapeutic Agents, Angew.Chem., Int. Ed. 2007, 46, 8748-8758. c) Rottmann M. et al.,Spiroindolones, a Potent Compound Class for the Treatmentof Malaria, Science 2010, 329, 1175-1180.
• Jia Z.-J., Zhou Q., Zhou Q.-Q., Chen P.-Q., Chen Y.-C, exo-Selective Asymmetric Diels–Alder Reaction of 2,4-Dienalsand Nitroalkenes by Trienamine Catalysis, Angew. Chem.,Int. Ed. 2011, 50, 8638-8641.[WoS]
• Jiang H., Gschwend B., Albrecht Ł., Hansen S. G., JørgensenK. A., Asymmetric Trienamine Catalysis for the Constructionof Structurally Rigid Cyclic α,α-Disubstituted Amino AcidDerivatives, Chem. Eur. J. 2011, 17, 9032-9036.[WoS]
• Liu Y., Nappi M., Erceo E., Vera S., Melchiorre P., AsymmetricCatalysis of Diels–Alder Reactions with in Situ GeneratedHeterocyclic ortho-Quinodimethanes, J. Am. Chem. Soc.2011, 133, 15212-15218.
• Liu Y., Nappi M., Escudero-Adán E. C., MelchiorreP., Multicatalytic Asymmetric Synthesis of ComplexTetrahydrocarbazoles via a Diels–Alder/Benzoin ReactionSequence, Org. Lett. 2012, 14, 1310-1313.
• Xiong X.-F., Zhou Q., Gu J., Dong L., Liu T.-Y., Chen Y.-C.,Trienamine Catalysis with 2,4-Dienones: Development andApplication in Asymmetric Diels–Alder Reactions, Angew.Chem., Int. Ed. 2012, 51, 4401–4404.[WoS]
• Halskov K. S., Johansen T. K., Davis R. L., SteurerM., Jensen F., Jørgensen K. A., Cross-trienamines inAsymmetric Organocatalysis, J. Am. Chem. Soc. 2012, 134,12943−12946.
• Dieckmann A., Breugst M. K., Houk N., Zwitterions andUnobserved Intermediates in Organocatalytic Diels–AlderReactions of Linear and Cross-Conjugated Trienamines, J.Am. Chem. Soc. 2013, 135, 3237−3242.[WoS]
• Albrecht L., Acosta F. C., Fraile A., Albrecht A.,Christensen J., Jørgensen K. A., Enantioselective H-Bond-Directing Approach for Trienamine-mediated Reactions inAsymmetric Synthesis, Angew. Chem., Int. Ed. 2012, 51,9088-9092.[WoS]
• For a review in squaramide catalysis, see: Alemán J., ParraA., Jiang H., Jørgensen K. A., Squaramides: Bridging fromMolecular Recognition to Bifunctional Organocatalysis,Chem. Eur. J. 2011, 17, 6890–6899.
• Jiang H., Rodríguez-Escrich C., Johansen T. K., DavisR. L., Jørgensen K. A., Organocatalytic Activation of Polycyclic Aromatic Compounds for Asymmetric Diels–Alder Reactions, Angew. Chem., Int. Ed. 2012, 51, 10271-10274.[WoS]
• Rodríguez-Escrich C., Davis R. L., Jiang H., Stiller J.,Johansen, T. K., Jørgensen K. A., Breaking Symmetrywith Symmetry: Bifacial Selectivity in the AsymmetricCycloaddition of Anthracene Derivatives, Chem. Eur. J. 2012,19, 2932-2936.
• Zhu K., Huang H., Wu W., Wei Y., Ye J., AminocatalyzedAsymmetric Diels–Alder Reaction of 2,4-Dienals andRhodanine/hydantoin Derivatives, Chem. Commun. 2013,49, 2157-2159.[WoS]
• Zhang S.-J., Zhang J., Zhou Q.-Q., Dong L., Chen Y.-C.,Aminocatalytic Asymmetric exo-Diels–Alder Reaction withMethiodide Salts of Mannich Bases and 2,4-Dienals toConstruct Chiral Spirocycles, Org. Lett. 2013, 15, 968-971.[WoS]

Identifiers

DOI

10.2478/asorg-2013-0001