A Tandem Sulfonylation and Knoevenagel Condensation for the Preparation of Sulfocoumarin-3-carboxylates

Ziyang Dong; Yang Chen; Zhiheng Yang; Zhanhui Yang; Jiaxi Xu

doi:10.1055/s-0037-1611703

Synthesis, Table of Contents

Synthesis 2019; 51(08): 1809-1818
DOI: 10.1055/s-0037-1611703

paper

A Tandem Sulfonylation and Knoevenagel Condensation for the Preparation of Sulfocoumarin-3-carboxylates

Authors

Ziyang Dong ‡

^aState Key Laboratory of Chemical Resource Engineering, Department of Organic Chemistry, College of Science, Beijing University of Chemical Technology, Beijing 100029, P. R. of China Email: zhyang@mail.buct.edu.cn Email: jxxu@mail.buct.edu.cn
Yang Chen ‡

^aState Key Laboratory of Chemical Resource Engineering, Department of Organic Chemistry, College of Science, Beijing University of Chemical Technology, Beijing 100029, P. R. of China Email: zhyang@mail.buct.edu.cn Email: jxxu@mail.buct.edu.cn
Zhiheng Yang

^bDepartment of Pharmacy, The First Affiliated Hospital, Zhengzhou University, Zhengzhou 450052, P. R. of China
Zhanhui Yang *

^aState Key Laboratory of Chemical Resource Engineering, Department of Organic Chemistry, College of Science, Beijing University of Chemical Technology, Beijing 100029, P. R. of China Email: zhyang@mail.buct.edu.cn Email: jxxu@mail.buct.edu.cn
Jiaxi Xu*

^aState Key Laboratory of Chemical Resource Engineering, Department of Organic Chemistry, College of Science, Beijing University of Chemical Technology, Beijing 100029, P. R. of China Email: zhyang@mail.buct.edu.cn Email: jxxu@mail.buct.edu.cn

Abstract

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^‡ These authors contributed equally to this work.

Abstract

Sulfocoumarins are key structural motifs in several bioactive molecules. Herein, we describe a simple, one-pot procedure for the synthesis of structurally diverse sulfonocoumarin-3-carboxylates by heating 2-hydroxyaryl aldehydes with an active sulfonyl chloride in the presence of pyridine. The process tolerates numerous functional groups including alkoxy, alkyl, halogen, nitro, and even nucleophilic phenolic hydroxy. Additionally, reactions of 2-hydroxyaryl ketones and 2-methylaminoaryl aldehydes give 4-substituted sulfocoumarins and 1-aza-2-sulfocoumarins, respectively. A gram-scale synthesis and further derivatizations are also reported. The ester group is easily removed via Happer’s decarboxylation.

Key words

sulfocoumarin-3-carboxylates - tandem reactions - sulfonylation - Knoevenagel condensation - salicylaldehyde

Full Text

References

References
1 Tanc M, Carta F, Bozdag M, Scozzafava A, Supuran CT. Bioorg. Med. Chem. 2013; 21: 4502
2 Grandane A, Tanc M, Zalubovskis R, Supuran CT. Bioorg. Med. Chem. Lett. 2014; 24: 1256

3a Grandane A, Tanc M, Zalubovskis R, Supuran CT. Bioorg. Med. Chem. 2014; 22: 1522
3b Tars K, Vullo D, Kazaks A, Leitans J, Lends A, Grandane A, Zalubovskis R, Scozzafava A, Supuran CT. J. Med. Chem. 2013; 56: 293

4 Grandane A, Tanc M, Zalubovskis R, Supuran CT. Bioorg. Med. Chem. 2015; 23: 1430
5 Grandane A, Tanc M, Di Cesare Mannelli L, Carta F, Ghelardini C, Zalubovskis R, Supuran CT. J. Med. Chem. 2015; 58: 3975
6 Tanc M, Carta F, Scozzafava A, Supuran CT. Org. Biomol. Chem. 2015; 13: 77

7a Kim N, Min M, Hong S. Org. Chem. Front. 2015; 2: 1621
7b Alcaide B, Almendros P, Aragoncillo C, Fernandez I, Gomez-Campillos G. Chem. Eur. J. 2016; 22: 285

8 Hoogenboom BE, El-Faghi MS, Fink SC, Ihrig PJ, Langsjoen AN, Linn CJ, Maehling KL. J. Org. Chem. 1975; 40: 880
9 Ghandi M, Bozcheloei AH, Nazari SH, Sadeghzadeh M. J. Org. Chem. 2011; 76: 9975
10 Edwards DJ, Hadfield JA, Wallace TW, Ducki S. Org. Biomol. Chem. 2011; 9: 219
11 Grandane A, Belyakov S, Trapencieris P, Zalubovskis R. Tetrahedron 2012; 68: 5541

12a Yang Z, Xu J. Synthesis 2013; 45: 1675
12b Yang Z, Zheng Y, Xu J. Synlett 2013; 24: 2165
12c Yang Z, Zhou B, Xu J. Synthesis 2014; 46: 225
12d Yang Z, Xu J. Org. Synth. 2014; 91: 116
12e Yang Z, Xu W, Wu Q, Xu J. J. Org. Chem. 2016; 81: 3051
12f Yang Z, Yang S, Xu J. Tetrahedron 2017; 73: 3240
12g Yang Z, Yang S, Haroone MS, He W, Xu J. Tetrahedron 2017; 73: 3338

13a Yang Z, Xu J. J. Org. Chem. 2014; 79: 10703
13b Yang Z, Chen N, Xu J. J. Org. Chem. 2015; 80: 3611
13c Yang Z, Xu J. Tetrahedron 2015; 71: 2844
13d Yang Z, Xu J. RSC Adv. 2015; 5: 78396
13e Yang Z, Abdellaoui H, He W, Xu J. Molecules 2017; 22: 784
13f Xu W, Fu Z, Yang Z, Zhang L, Xu J. Phosphorus, Sulfur Silicon Relat. Elem. 2018; 193: 335

14a Yang Z, Xu J. Chem. Commun. 2014; 50: 3616
14b Huang P, Yang Z, Xu J. Tetrahedron 2017; 73: 3255

15 Cecchi L, De Sarlo F, Machetti F. Eur. J. Org. Chem. 2006; 21: 4852
16 See: https://en.wikipedia.org/wiki/Non-nucleophilic_base (accessed Dec 21st, 2018).
17 Rodima T, Kaljurand I, Pihl A, Maeemets V, Leito I, Koppel IA. J. Org. Chem. 2002; 67: 1873
18 Brown HC, McDaniel DH, Häfliger O. Dissociation Constants . In Determination of Organic Structures by Physical Methods . Braude EA, Nachod FC. Academic Press; New York: 1955
19 Linnell RH. J. Org. Chem. 1960; 25: 290
20 Wei Y, Sastry GN, Zipse H. J. Am. Chem. Soc. 2008; 130: 3473
21 For sulfene generation and as related mechanism, see refs. 13d, 13e, and 13f, and references cited therein.
22 Gawron O, Duggan M, Grelechi CJ. Anal. Chem. 1952; 24: 969

23a McGeachin SG. Can. J. Chem. 1966; 44: 2323
23b Pieta M, Kedzia J, Janecka A, Pomorska DK, Rozalski M, Krajewska U, Janecki T. RSC Adv. 2015; 5: 78324
23c Albert A, Yamamoto H. J. Chem. Soc. B: Phys. Org. 1966; 956
23d Sridharan V, Ribelles P, Ramos MT, Menendez JC. J. Org. Chem. 2009; 74: 5715
23e Younes EA, Hussein AQ, May MA, Fronczek FR. ARKIVOC 2011; (ii): 322
23f Pettersson B, Bergman J, Svensson PH. Tetrahedron 2013; 69: 2647

24 Shyshkina OO, Tkachuk TM, Volovnenko TA, Volovenko YM, Zubatyuk RI, Medviediev VV, Shishkin OV. Tetrahedron Lett. 2012; 53: 4296
25 Jadhav MM, Vaghasiya JV, Patil DS, Soni SS, Sekar N. New J. Chem. 2018; 42: 5267
26 Happer DA. R, Steenson BE. Synthesis 1980; 806

Supplementary Material

Supporting Information (PDF)