Download PDF
Synthesis 2024; 56(03): 455-461
DOI: 10.1055/a-2204-2801
paper

A Formal Exchange Reaction between Ketones and Vinyl Ethers with Solid Catalysts

Paloma Mingueza-Verdejo
a   Universitat Politècnica de València- Agencia Estatal Consejo Superior de Investigaciones Científicas, Avda. de los Naranjos s/n, 46022 Valencia, Spain
,
Jose Pedro Cerón-Carrasco
b   Centro Universitario de la Defensa, Academia General del Aire, Universidad Politécnica de Cartagena, C/ Coronel López Peña S/N, Santiago de La Ribera, 30720 Murcia, Spain
,
Judit Oliver-Meseguer∗
a   Universitat Politècnica de València- Agencia Estatal Consejo Superior de Investigaciones Científicas, Avda. de los Naranjos s/n, 46022 Valencia, Spain
,
Antonio Leyva-Pérez∗
a   Universitat Politècnica de València- Agencia Estatal Consejo Superior de Investigaciones Científicas, Avda. de los Naranjos s/n, 46022 Valencia, Spain
› Author AffiliationsFinancial support by Severo Ochoa centre of excellence program (CEX2021-001230-S) is gratefully acknowledged. Financial support by Spanish MICIIN (project code PID2020-115100GB-I00) and Generalitat Valenciana (GV/2021/138) are also acknowledged.
› Further Information
    Permissions and Reprints All articles of this category


Abstract

The formal exchange of functional groups in internal positions of two different molecules is of interest in synthetic chemistry, as a simple retrosynthetic strategy. Here the formal exchange reaction between internal α-methylene ketones and vinyl ethers, retaining the original C–O bonds is presented. This process offers a new route for the synthesis of vinyl ethers in one step from ketones, including 1,3-diketones, under mild reaction conditions. Besides, the reaction is catalyzed by reusable cheap solids and can be carried out in flow for 20 days without signs of catalyst depletion. Combined experimental and computational mechanistic studies unveil the key role of carbonyl–enol equilibria.

Key words

solid catalyst - vinyl ether - ketone - exchange reaction - reaction in flow

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/a-2204-2801.
  • Supporting Information


Publication History

Received: 17 May 2023

Accepted after revision: 03 November 2023

Accepted Manuscript online:
03 November 2023

Article published online:
05 December 2023

© 2023. Thieme. All rights reserved

Georg Thieme Verlag KG
Rüdigerstraße 14, 70469 Stuttgart, Germany

 

  • References

  • 1 Rivero-Crespo M. Á, Tejeda-Serrano M, Pérez-Sánchez H, Cerón-Carrasco JP, Leyva-Pérez A. Angew. Chem. Int. Ed. 2020; 59: 3846
    CrossrefPubMed
  • 2 Song JJ, Tan Z, Reeves JT, Fandrick DR, Yee NK, Senanayake CH. Org. Lett. 2008; 10: 877
    CrossrefPubMed
  • 3 Lewis JD, Van de Vyver S, Román-Leshkov Y. Angew. Chem. Int. Ed. 2015; 54: 9835
    CrossrefPubMed
  • 4 Ludwig JR, Watson RB, Nasrallah DJ, Gianino JB, Zimmerman PM, Wiscons RA, Schindler CS. Science 2018; 361: 1363
    CrossrefPubMed
  • 5 Catti L, Tiefenbacher K. Angew. Chem. Int. Ed. 2018; 57: 14589
    CrossrefPubMed
  • 6 Bae HY, Höfler D, Kaib PS. J, Kasaplar P, De CK, Döhring A, Lee S, Kaupmees K, Leito I, List B. Nat. Chem. 2018; 10: 888
    CrossrefPubMed
  • 7 Griffith AK, Vanos CM, Lambert TH. J. Am. Chem. Soc. 2012; 134: 18581
    CrossrefPubMed
  • 8 Ludwig JR, Zimmerman PM, Gianino JB, Schindler CS. Nature 2016; 533: 374
    CrossrefPubMed
  • 9 Bhawal BN, Morandi B. Angew. Chem. Int. Ed. 2019; 58: 10074
    CrossrefPubMed
  • 10 Bender TA, Payne PR, Gagné MR. Nat. Chem. 2018; 10: 85
    CrossrefPubMed
  • 11 McNally A. Nat. Chem. 2015; 7: 539
    CrossrefPubMed
  • 12 Śliwa M, Samson K, Ruggiero-Mikołajczyk M, Żelazny A, Grabowski R. Catal. Lett. 2014; 144: 1884
    Crossref
  • 13 Mougel V, Chan K.-W, Siddiqi G, Kawakita K, Nagae H, Tsurugi H, Mashima K, Safonova O, Copéret C. ACS Cent. Sci. 2016; 2: 569
    CrossrefPubMed
  • 14 Korzyński MD, Consoli DF, Zhang S, Román-Leshkov Y, Dincă M. J. Am. Chem. Soc. 2018; 140: 6956
    CrossrefPubMed
  • 15 Copéret C, Allouche F, Chan KW, Conley MP, Delley MF, Fedorov A, Moroz IB, Mougel V, Pucino M, Searles K, Yamamoto K, Zhizhko PA. Angew. Chem. Int. Ed. 2018; 57: 6398
    CrossrefPubMed
  • 16 Garnes-Portolés F, Greco R, Oliver-Meseguer J, Castellanos-Soriano J, Consuelo Jiménez M, López-Haro M, Hernández-Garrido JC, Boronat M, Pérez-Ruiz R, Leyva-Pérez A. Nat. Catal. 2021; 4: 293
    Crossref
  • 17 Oliver-Meseguer J, Ballesteros-Soberanas J, Tejeda-Serrano M, Martínez-Castelló A, Leyva-Pérez A. Mol. Catal. 2021; 515: 111927
    Crossref
  • 18 Tejeda-Serrano M, Mon M, Ross B, Gonell F, Ferrando-Soria J, Corma A, Leyva-Pérez A, Armentano D, Pardo E. J. Am. Chem. Soc. 2018; 140: 8827
    CrossrefPubMed
  • 19 Tiburcio E, Greco R, Mon M, Ballesteros-Soberanas J, Ferrando-Soria J, López-Haro M, Hernández-Garrido JC, Oliver-Meseguer J, Marini C, Boronat M, Armentano D, Leyva-Pérez A, Pardo E. J. Am. Chem. Soc. 2021; 143: 2581
    CrossrefPubMed
  • 20 Mohanta N, Chaudhari MB, Digrawal NK, Gnanaprakasam B. Org. Process Res. Dev. 2019; 23: 1034
    Crossref
  • 21 Yang B, Dai J, Luo Y, Lau KK, Lan Y, Shao Z, Zhao Y. J. Am. Chem. Soc. 2021; 143: 4179
    CrossrefPubMed
  • 22 Ding W, Chai J, Wang C, Wu J, Yoshikai N. J. Am. Chem. Soc. 2020; 142: 8619
    CrossrefPubMed
  • 23 Cao HT, Grée R. Tetrahedron Lett. 2009; 50: 1493
    Crossref
  • 24 Nayyar S, Trehan I, Kaur J. Indian J. Chem., Sect. B: Org. Chem. Incl. Med. Chem. 2002; 41: 2342
  • 25 Bohm A, Batch T. Chem. Eur. J. 2016; 22: 15921
    CrossrefPubMed
  • 26 Wang X, Liu R, Jin Y, Liang X. Chem. Eur. J. 2008; 14: 2679
    CrossrefPubMed