Synthesis
DOI: 10.1055/s-0037-1612376
paper
© Georg Thieme Verlag Stuttgart · New York

Microwave-Assisted Cyclization of Unprotected Dipeptides in Water to 2,5-Piperazinediones and Self-Assembly Study of Products­ and Reagents

Marina Kurbasic
a  Chemical & Pharmaceutical Sciences Dept., University of Trieste, Via L. Giorgieri 1, 34127 Trieste, Italy
,
Sabrina Semeraro
a  Chemical & Pharmaceutical Sciences Dept., University of Trieste, Via L. Giorgieri 1, 34127 Trieste, Italy
,
Ana M. Garcia
a  Chemical & Pharmaceutical Sciences Dept., University of Trieste, Via L. Giorgieri 1, 34127 Trieste, Italy
,
Slavko Kralj
a  Chemical & Pharmaceutical Sciences Dept., University of Trieste, Via L. Giorgieri 1, 34127 Trieste, Italy
b  Materials Synthesis Department, Jožef Stefan Institute, Jamova 39, 1000 Ljubljana, Slovenia   Email: smarchesan@units.it
,
Evelina Parisi
a  Chemical & Pharmaceutical Sciences Dept., University of Trieste, Via L. Giorgieri 1, 34127 Trieste, Italy
,
Caterina Deganutti
a  Chemical & Pharmaceutical Sciences Dept., University of Trieste, Via L. Giorgieri 1, 34127 Trieste, Italy
,
Rita De Zorzi
a  Chemical & Pharmaceutical Sciences Dept., University of Trieste, Via L. Giorgieri 1, 34127 Trieste, Italy
,
a  Chemical & Pharmaceutical Sciences Dept., University of Trieste, Via L. Giorgieri 1, 34127 Trieste, Italy
› Author Affiliations
Italian Ministry of University and Research (MIUR) through the Scientific Independence of Young Researchers (SIR) program (‘HOT-SPOT’ project, personal research grant no. RBSI14A7PL to S.M.), Ramón Areces Foundation (A.M.G.’s fellowship), and Beneficentia Stiftung Fundation.
Further Information

Publication History

Received: 03 February 2019

Accepted after revision: 08 March 2019

Publication Date:
25 March 2019 (eFirst)

Published as part of the Bürgenstock Special Section 2018 Future Stars in Organic Chemistry

Abstract

Dipeptides and their cyclized 2,5-piperazinedione (or diketopiperazine, DKP) derivatives are attractive building blocks for supra­molecular hydrogels. The Phe-Phe, (p-nitro)-Phe-Phe, and Phe-Val dipeptides and their corresponding DKPs are studied for self-assembly in water. The DKPs were obtained in high yields by microwave-assisted cyclization­ of the dipeptides in water, demonstrating that use of their methyl ester derivatives as reported in the literature is not necessary for successful cyclization. Single-crystal XRD structures are reported for two DKPs as well as stable hydrogels at neutral pH.

Supporting Information

 
  • References

  • 1 Reches M, Gazit E. Science 2003; 300: 625
  • 2 Chen J, Qin S, Wu X, Chu PK. ACS Nano 2016; 10: 832
  • 3 Yuran S, Razvag Y, Reches M. ACS Nano 2012; 6: 9559
  • 4 Marchesan S, Vargiu AV, Styan KE. Molecules 2015; 20: 19775
  • 5 Melchionna M, Styan KE, Marchesan S. Curr. Top. Med. Chem. 2016; 16: 2009
  • 6 Orbach R, Mironi-Harpaz I, Adler-Abramovich L, Mossou E, Mitchell EP, Forsyth VT, Gazit E, Seliktar D. Langmuir 2012; 28: 2015
  • 7 Martin AD, Wojciechowski JP, Warren H, in het Panhuis M, Thordarson P. Soft Matter 2016; 12: 2700
  • 8 Liyanage W, Nilsson BL. Langmuir 2016; 32: 787
  • 9 Conte MP, Singh N, Sasselli IR, Escuder B, Ulijn RV. Chem. Commun. 2016; 52: 13889
  • 10 Chen Y, Li X, Bai J, Shi F, Xu T, Gong Q, Yang Z. Chem. Commun. 2018; 54: 11721
  • 11 Diaferia C, Gianolio E, Accardo A, Morelli G. J. Pep. Sci. 2017; 23: 122
    • 12a Tesauro D, Accardo A, Diaferia C, Milano V, Guillon J, Ronga L, Rossi F. Molecules 2019; 24: 351
    • 12b Parisi E, Garcia AM, Marson D, Posocco P, Marchesan S. Gels 2019; 5: 5
    • 12c Kurbasic M, Romano CD, Garcia AM, Kralj S, Marchesan S. Gels 2017; 3: 29
    • 13a Yang X, Wang Y, Qi W, Su R, He Z. Nanoscale 2017; 9: 15323
    • 13b Garcia AM, Kurbasic M, Kralj S, Melchionna M, Marchesan S. Chem. Commun. 2017; 53: 8110
  • 14 Araújo M, Muñoz CapdevilaI, Díaz-Oltra S, Escuder B. Molecules 2016; 21: 744
  • 15 Borthwick AD. Chem. Rev. 2012; 112: 3641
  • 16 Liao S, Qin X, Li D, Tu Z, Li J, Zhou X, Wang J, Yang B, Lin X, Liu J, Yang X, Liu Y. Eur. J. Med. Chem. 2014; 83: 236
  • 17 Zong L, Bartolami E, Abegg D, Adibekian A, Sakai N, Matile S. ACS Cent. Sci. 2017; 3: 449
  • 18 Ying J, Lin R, Xu P, Wu Y, Liu Y, Zhao Y. Sci. Rep. 2018; 8: 936
  • 19 Manchineella S, Govindaraju T. ChemPlusChem 2017; 82: 88
    • 20a Pérez-Picaso L, Escalante J, Olivo HF, Rios MY. Molecules 2009; 14: 2836
    • 20b López-Cobeñas A, Cledera P, Sánchez JD, López-Alvarado P, Ramos MT, Avendaño C, Menéndez JC. Synthesis 2005; 3412
  • 21 Tullberg M, Grøtli M, Luthman K. Tetrahedron 2006; 62: 7484
    • 22a Vahdati L, Fanelli R, Bernadat G, Correia I, Lequin O, Ongeri S, Piarulli U. New J. Chem. 2015; 39: 3250
    • 22b Airaghi F, Fiorati A, Lesma G, Musolino M, Sacchetti A, Silvani A. Beilstein J. Org. Chem. 2013; 9: 147
    • 22c Marchini M, Mingozzi M, Colombo R, Guzzetti I, Belvisi L, Vasile F, Potenza D, Piarulli U. Chem. Eur. J. 2012; 18: 6195
  • 23 Gdaniec M, Liberek B. Acta Crystallogr., Sect. C 1986; 42: 1343
  • 24 Corey RB. J. Am. Chem. Soc. 1938; 60: 1598
    • 25a Garcia AM, Iglesias D, Parisi E, Styan KE, Waddington LJ, Deganutti C, De Zorzi R, Grassi M, Melchionna M, Vargiu AV, Marchesan S. Chem 2018; 4: 1862
    • 25b Vargiu AV, Iglesias D, Styan KE, Waddington LJ, Easton CD, Marchesan S. Chem. Commun. 2016; 52: 5912
  • 26 Govindaraju T. Supramol. Chem. 2011; 23: 759
  • 27 Sulatskaya AI, Kuznetsova IM, Turoverov KK. J. Phys. Chem. B 2011; 115: 11519
  • 28 Cringoli MC, Kralj S, Kurbasic M, Urban M, Marchesan S. Beilstein J. Nanotechnol. 2017; 8: 1553
  • 29 Kabsch W. Acta Crystallogr., Sect. D 2010; 66: 125
  • 30 Evans PR. Acta Crystallogr., Sect. D 2006; 62: 72
  • 31 Evans PR, Murshudov GN. Acta Crystallogr., Sect. D 2013; 69: 1204
  • 32 Sheldrick GM. Acta Crystallogr., Sect. A 2008; (Pt 1): 64-112
  • 33 Sheldrick GM. Acta Crystallogr., Sect. C 2015; 71: 3
  • 34 Farrugia LJ. J. Appl. Crystallogr. 2012; 45: 849
  • 35 CCDC 1895316 (DKP1) and 1895262 (DKP2) contain the supplementary crystallographic data for this paper. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/getstructures.