1. Transition Metal-Catalyzed Asymmetric Construction of Heterocyclic Compounds

  • Dipolar cycloadditions are one the most efficient methodologies for the preparation of five- membered heterocycles owing to their ability to generate complex molecules in a stereocontrolled way, largely meeting sustainability requirements. A broad scope of (hetero)cycles can be prepared depending on the dipole and dipolarophile employed. The effective control of the regio- and diastereoselectivity achieved in these transformations have been key factors of their synthetic usefulness. In addition, the catalytic asymmetric version of these transformations constitutes a powerful methodology to access heterocyclic motifs in a highly enantioenrich manner.

 

  • Selected publications of this research line:

 

1. Atroposelective Synthesis of Axially Chiral Naphthylpyrroles by a Catalytic Asymmetric
1,3-Dipolar Cycloaddition/Aromatization Sequence
Ian Maclean, Enrique Gallent, Oscar Orozco, Alba Molina, Nuria Rodríguez, Javier Adrio,
Juan C. Carretero Org. Lett. 2024, 26, 922-927.

DOI:10.1021/acs.orglett.3c04261

 

2. Delta-Amination of Alkyl Alcohols via Energy Transfer Photocatalysis

Cristobal C, Alonso I, Cabrera-Afonso MJ, Adrio J, Ribagorda M.

ChemRxiv. (2024);

DOI: 10.26434/chemrxiv-2024-zt1xl


This content is a preprint and has not been peer-reviewed.

 

3. Sulfenate Anion Catalyzed Diastereoselective Synthesis of Aziridines

Zhipeng Zheng, Youge Pu, Javier Adrio, Patrick J. Walsh

Angew. Chem. Int. 62, e202303069 (2023).

DOI: 10.1002/anie.202303069

 

4. Enantioselective transformations of 5-hydroxymethylfurfural via catalytic asymmetric 1,3-dipolar cycloaddition of azomethine ylides.

Christian Cristóbal, César Corral, Juan C. Carretero, Maria Ribagorda, Javier Adrio

Chemical Commun. 59, 4336-4339 (2023).

DOI: 10.1039/d3cc00499f

 

5. Catalytic enantioselective intramolecular 1,3-dipolar cycloaddition of azomethine ylides with fluorinated dipolarophiles

Christian Cristóbal, Daniel Gaviña, Inés Alonso, María Ribagorda, Juan C. Carretero, Carlos del Pozo, Javier Adrio

Chem. Commun. 58, 7805-7808 (2022).

DOI: 10.1039/d2cc02902b

 

6. Catalyst-Controlled Chemodivergent [3+3] and [3+2] Formal Cycloadditions of Azomethine Ylides with Diphenylcyclopropenone

Javier Corpas, Alberto Ponce, Ian Maclean, Javier Adrio, Juan C. Carretero

Synthesis. 54, 4673-4682 (2022).

DOI: 10.1055/a-1829-0262

 

7. Metal-Free Solvent Promoted Oxidation of Benzylic Secondary Amines to Nitrones with H2O2

Álisson Silva Granato, Giovanni Wilson Amarante, Javier Adrio

J. Org. Chem. 86, 13817–13823 (2021).

DOI: 10.1021/acs.joc.1c01888

 

8.  Aldehydes as Photoremovable Directing Groups: Synthesis of Pyrazoles by a Photocatalyzed [3+2] Cycloaddition/Norrish Type Fragmentation Sequence

Ana Pascual-Escudero, Laura Ortiz-Rojano, Silvia Simón-Fuente, Javier Adrio, María Ribagorda

Org. Lett. 23, 4903−4908 (2021).

DOI: 10.1021/acs.orglett.1c01665

 

9. On the mixed oxides-supported niobium catalyst towards benzylamine oxidation

Alisson Silva Granato, Gustavo S. Gonçalves de Carvalho, Carla G. Fonseca, Javier Adrio, Alexandre A. Leitao, Giovanni Wilson Amarante

Catalysis Today. 381, 118–125 (2020).

DOI: 10.1016/j.cattod.2020.08.011

 

10. Catalytic Asymmetric Synthesis of Diazabicyclo[3.1.0]hexanes by 1,3-Dipolar Cycloaddition of Azomethine Ylides with Azirines‎

Alba Molina, Sergio Diaz-Tendero, Javier Adrio, Juan C. Carretero

Chem. Commun. 5, 5050–5053 (2020).

DOI: 10.1039/d0cc01061h

 

11. Stereochemical Diversity in Pyrrolidine Synthesis by Catalytic Asymmetric 1,3-Dipolar cycloaddition of Azomethine Ylides

Javier Adrio, Juan C. Carretero

Chem. Commun. 55, 11979–11991(2019).

DOI: 10.1039/c9cc05238k

 

12. Cu(I)-Catalyzed Asymmetric [3+2] Cycloaddition of Azomethine Ylides with Cyclobutenones

Javier Corpas, Alberto Ponce, Javier Adrio, Juan C. Carretero

Org. Lett. 20, 3179–3182 (2018).

DOI: 10.1021/acs.orglett.8b00936

 

13. Catalytic Asymmetric 1,3-Dipolar Cycloaddition/Hydroamination Sequence: Expeditious Access to Enantioenriched Pyrroloisoquinoline Derivatives.

Alba Molina, Ana Pacual-Escudero, Javier Adrio, Juan Carlos Carretero

J. Org Chem. 82, 11238-11246 (2017).

DOI: 10.1021/acs.joc.7b01927

 

14. Transition-metal-free chemo- and regioselective vinylation of azaallyls.

Minyan, Li, Osvaldo Gutierrez, Simon Berritt, Ana Pascual-Escudero, Ahmet Yesilcimen, Xiaodong Yang, Javier Adrio, Georgia Huang, Eiko, Nakamaru-Ogiso, Marisa C. Kozlowski, Patrick J. Walsh

Nat. Chem. 9, 997-1004 (2017).

DOI: 10.1038/nchem.2760

 

15. Alkenylarenes as Dipolarophiles in Catalytic Asymmetric 1,3-Dipolar Cycloaddition of Azomethine Ylides.

Ana Pascual-Escudero, Abel de Cózar, Fernando P. Cossío, Javier Adrio, Juan Carlos Carretero

Angew. Chem. Int. Ed. 55,15334-15338 (2016).

DOI: 10.1002/anie.201609187

 

16. Stereoselective Ag-Catalyzed 1,3-Dipolar Cycloaddition of Activated Trifluoromethyl-Substituted Azomethine Ylides.

Alberto Ponce, Inés Alonso, Javier Adrio, and Juan C. Carretero

Chem Eur. J. 22, 4952-4959 (2016).

DOI: 10.1002/chem.201504869

 

17. Highly Selective Copper-Catalyzed Asymmetric [3+2] Cycloaddition of Azomethine Ylides with Acyclic 1,3-Dienes.

María González-Esguevillas, Ana Pascual-Escudero, Javier Adrio, and Juan C. Carretero. Chem. Eur. J. 21, 4561-4565 (2015).

DOI: doi.org/10.1002/chem.201500182

 

18. Synthesis of diarylmethylamines via palladium-catalyzed regioselective arylation of 1,1,3-triaryl-2-azaallyl anions.

Minyan Li, Baris Yücel, Javier Adrio, Ana Bellomo, Patrick J. Walsh

Chem. Sci. 5, 2383-2391 (2014).

DOI: 10.1039/C3SC53526F

 

19. Enantioselective Synthesis of α-Heteroarylpyrrolidines by Copper-Catalyzed 1,3-Dipolar Cycloaddition of α-Silylimines.

Ana Pascual-Escudero, María González-Esguevillas, Silvia Padilla, Javier Adrio, and Juan C. Carretero.

Org. Lett. 16, 2228-2231(2014).

DOI: 10.1021/ol5007373

 

20. Catalytic Asymmetric Synthesis of α-Quaternary Proline Derivatives by 1,3-Dipolar Cycloaddition of α-Silylimines.

Jorge Hernández Toribio, Silvia Padilla, Javier Adrio, Juan Carlos Carretero

Angew. Chem. Int. Ed. 51, 8854-8858 (2012).

DOI: 10.1002/anie.201203828

 

21. Phenylsulfonyl Group as Temporal Regiochemical Controller in Catalytic Asymetric 1,3-Dipolar Cycloaddition of Azomethine Ylides.

Ana López-Pérez, Javier Adrio, Juan Carlos Carretero.

Angew. Chem. Int. Ed. 48, 340-343 (2009).

DOI: 10.1002/anie.200805063