A New General Synthesis of 2,5-Disubstituted Thiophenes Starting From β-Nitro-β,γ-Unsaturated Ketones and 4-Methoxybenzyl Mercaptan

Eleonora Bentivogli; Iqra Munir; Muhammad E. I. Khan; Roberto Ballini; Marino Petrini; Alessandro Palmieri

doi:10.1055/a-2714-8785

Synthesis, Table of Contents

Synthesis
DOI: 10.1055/a-2714-8785

Paper

A New General Synthesis of 2,5-Disubstituted Thiophenes Starting From β-Nitro-β,γ-Unsaturated Ketones and 4-Methoxybenzyl Mercaptan

Authors

Eleonora Bentivogli

¹Green Chemistry Group, School of Sciences and Technology, Chemistry Division, University of Camerino, Camerino (MC), Italy
Iqra Munir

¹Green Chemistry Group, School of Sciences and Technology, Chemistry Division, University of Camerino, Camerino (MC), Italy
Muhammad E. I. Khan

¹Green Chemistry Group, School of Sciences and Technology, Chemistry Division, University of Camerino, Camerino (MC), Italy
Roberto Ballini

¹Green Chemistry Group, School of Sciences and Technology, Chemistry Division, University of Camerino, Camerino (MC), Italy
Marino Petrini

¹Green Chemistry Group, School of Sciences and Technology, Chemistry Division, University of Camerino, Camerino (MC), Italy
Alessandro Palmieri

¹Green Chemistry Group, School of Sciences and Technology, Chemistry Division, University of Camerino, Camerino (MC), Italy

Abstract

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Abstract

Herein, we report a practical synthesis of 2,5-disubstituted thiophenes. The protocol features an initial base-promoted Michael addition of 4-methoxybenzyl mercaptan to β-nitro-β,γ-unsaturated ketones, followed by an acid-mediated cyclization of the resulting adducts. This one-pot procedure affords the desired thiophene derivatives in good overall yields.

Keywords

Thiophene - Nitroalkenes - Conjugate addition - Cyclization - Aromatization

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References

References

1a Roncali J. Chem Rev 1992; 92: 717-738
1b Cinar ME, Ozturk T. Chem Rev 2015; 115: 3036-3140
1c Keri RS, Chand K, Budagumpi S, Balappa SS, Patil SA, Nagaraja BM. Eur J Med Chem 2017; 138: 1002-1033
1d Barbarella G, Zangoli M, Di Maria F. Adv Heterocycl Chem 2017; 123: 105-167
1e da Cruz RMD, Mendonça-Junior FJB, de Mélo NB. et al. Pharmaceuticals 2021; 14: 692
1f Ibrahim SRM, Omar AM, Bagalagel AA. et al. Plants 2022; 11: 539
1g Chawla S, Sharma S, Kashid S, Verma PK, Sapra A. Mini Rev Med Chem 2023; 23: 1514-1534

2a Brettle R, Dunmur DA, Marson CM, Piñol M, Toriyama K. Chem Lett 1992; 4: 613-616
2b Campbell NL, Duffy WL, Thomas GI. et al. J Mater Chem 2002; 12: 2706-2721
2c Panchamukhi SI, Belavagi N, Rabinal MH, Khazi IA. J Fluoresc 2011; 21: 1515-1519

3a Bayh O, Awad H, Mongin F. et al. Tetrahedron 2005; 61: 4779-4784
3b Battace A, Lemhadri M, Zair T, Douchet H, Santelli M. Adv Synth Catal 2007; 349: 2507-2516
3c Roger J, Doucet H. Org Biomol Chem 2008; 6: 169-174
3d Liégault B, Lapointe D, Caron L, Vlassova A, Fagnou K. J Org Chem 2009; 74: 1826-1834
3e Join B, Yamamoto T, Itami K. Angew Chem Int Ed 2009; 48: 3644-3647
3f Roger J, Požgan F, Douchet H. Green Chem 2009; 11: 425-432
3g Suhelen Vásquez-Céspedes S, Chepiga KM, Möller N, Schäfer AH, Glorius F. ACS Catal 2016; 6: 5954-5961
3h Liu L, Cordier M, Rosinel T, Doucet H. Org Chem Front 2023; 10: 1441-1455
3i Ohno A, Sato T, Mase T, Uozumi Y, Yamada YMA. Adv Synth Catal 2020; 362: 4687-4698

4a Shridhar DR, Jogibhukta M, Shanthan RP, Handa VK. Synthesis 1982; 12: 1061-1062
4b Seed AJ, Toyne KJ, Goodby JW. J Mater Chem 1995; 5: 653-661
4c Kiryanov AA, Sampson P, Seed AJ. J Org Chem 2001; 66: 7925-7929
4d Chen L, Min H, Zeng W. et al. Org Lett 2018; 20: 7392-7395
4e Chiurchiù E, Patehebieke Y, Gabrielli S, Ballini R, Palmieri A. Adv Synth Catal 2019; 361: 2042-2047
4f Li J, Liu Y, Chen Z. et al. J Org Chem 2022; 87: 3555-3556

5a Chiurchiù E, Xhafa S, Ballini R, Maestri G, Protti S, Palmieri A. Adv Synth Catal 2020; 362: 4680-4686
5b Lupidi G, Bassetti B, Ballini R, Petrini M, Palmieri A. Asian J Org Chem 2021; 10: 2334-2337
5c Khan MEI, Yuan L, Petrini M, Palmieri A. Synthesis 2023; 55: 3204-3208
5d Bassetti B, Ballini R, Petrini M, Palmieri A. Adv Synth Catal 2023; 365: 13-16
5e Khan MEI, Wang L, Bassetti B, Petrini M, Palmieri. Asian J Org Chem 2025; 14: e202500076

6a Ballini R, Palmieri A, Talaq MA, Gabrielli S. Adv Synth Catal 2009; 351: 2611-2614
6b Chiurchiù E, Gabrielli S, Ballini R, Palmieri A. Molecules 2019; 24: 4575

7 Jung ME, Koch P. Tetrahedron Lett 2011; 52: 6051-6054

8a Komiyama T, Minami Y, Furuya Y, Hiyama. Angew Chem Int Ed 2018; 57: 1987-1990
8b Mi C, Zhang B-B, Zhang G. et al. Chem Eur J 2024; 30: e202303857

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