Substrate-Controlled Regioselective Alkylation of 4-Hydroxycoumarin with Diazo Compounds through TfOH Catalysis

Zhimin Xia; Chunyan Li; Mengxiang Luo; Shuangxi Gu; Qiongjiao Yan; Jian Lv; Jie Zeng; Haifeng Wang

doi:10.1055/s-0043-1763637

Synlett, Inhaltsverzeichnis

Synlett 2024; 35(13): 1584-1590
DOI: 10.1055/s-0043-1763637

letter

Substrate-Controlled Regioselective Alkylation of 4-Hydroxycoumarin with Diazo Compounds through TfOH Catalysis

Zhimin Xia

^aPharmaceutical Research Institute, Wuhan Institute of Technology, Wuhan 430205, P. R. of China

^bSchool of Chemical Engineering & Pharmacy, Wuhan Institute of Technology, Wuhan 430205, P. R. of China

,

Chunyan Li

^aPharmaceutical Research Institute, Wuhan Institute of Technology, Wuhan 430205, P. R. of China

^bSchool of Chemical Engineering & Pharmacy, Wuhan Institute of Technology, Wuhan 430205, P. R. of China

,

Mengxiang Luo

^aPharmaceutical Research Institute, Wuhan Institute of Technology, Wuhan 430205, P. R. of China

^bSchool of Chemical Engineering & Pharmacy, Wuhan Institute of Technology, Wuhan 430205, P. R. of China

,

Shuangxi Gu

^aPharmaceutical Research Institute, Wuhan Institute of Technology, Wuhan 430205, P. R. of China

^bSchool of Chemical Engineering & Pharmacy, Wuhan Institute of Technology, Wuhan 430205, P. R. of China

^cKey Laboratory of Green Chemical Engineering Process of Ministry of Education, Wuhan 430205, P. R. of China

,

Qiongjiao Yan

^aPharmaceutical Research Institute, Wuhan Institute of Technology, Wuhan 430205, P. R. of China

,

Jian Lv

^aPharmaceutical Research Institute, Wuhan Institute of Technology, Wuhan 430205, P. R. of China

,

Jie Zeng

^aPharmaceutical Research Institute, Wuhan Institute of Technology, Wuhan 430205, P. R. of China

,

Haifeng Wang∗

^aPharmaceutical Research Institute, Wuhan Institute of Technology, Wuhan 430205, P. R. of China

^bSchool of Chemical Engineering & Pharmacy, Wuhan Institute of Technology, Wuhan 430205, P. R. of China

^cKey Laboratory of Green Chemical Engineering Process of Ministry of Education, Wuhan 430205, P. R. of China

› Institutsangaben

Abstract

Alle Artikel dieser Rubrik

Abstract

Control of the regioselectivity of nucleophiles toward alkylating agents is a fundamental problem in heterocyclic chemistry. Substrate-controlled TfOH-catalyzed alkylation of 4-hydroxycoumarin with diazo compounds has been developed to provide rapid access to the C3- or O-alkylated 4-hydroxycoumarins with high efficiency. The regioselectivity can be determined by varying the electronic nature of the diazo substrates, especially those bearing a methylthio group.

Key words

4-hydroxycoumarin - diazo compounds - metal-free catalysis - alkylation - regioselectivity

Volltext

Referenzen

References and Notes
1 Gomez-Outes A, Suarez-Gea ML, Calvo-Rojas G, Lecumberri R, Rocha E, Pozo-Hernandez C, Terleira-Fernandez AI, Vargas-Castrillon E. Curr. Drug Discovery Technol. 2012; 9: 83

2a Zhang J, Tan YL, Li GR, Chen LX, Nie MY, Wang ZH, Ji H. Molecules 2021; 26: 786
2b Stefanova TH, Nikolova NJ, Toshkova RA, Neychev HO. J. Exp. Ther. Oncol. 2007; 6: 107

3 Bizzarri BM, Botta L, Capecchi E, Celestino I, Checconi P, Palamara AT, Nencioni L, Saladino R. J. Nat. Prod. 2017; 80: 3248

4a Ong EB. B, Watanabe N, Saito A, Futamura Y, Abd El Galil KH, Koito A, Najimudin N, Osada H. J. Biol. Chem. 2011; 286: 14049
4b Wadhwa P, Jain P, Rudrawar S, Jadhav HR. A. Curr. Drug Discovery Technol. 2018; 15: 2

5a Pan L, Li X.-Z, Sun D.-A, Jin H, Guo H.-R, Qin B. Chin. Chem. Lett. 2016; 27: 375
5b Ellafi A, Farhat R, Snoussi M, Noumi E, Anouar E, Ben Ali R, El May MV, Sayadi S, Aouadi K, Kadri A, Ben Younes S. Int. J. Food Prop. 2023; 26: 1079

6a Bansal Y, Sethi P, Bansal G. Med. Chem. Res. 2013; 22: 3049
6b Mucha P, Skoczynska A, Malecka M, Hikisz P, Budzisz E. Molecules 2021; 26: 4886

7a Cheke RS, Patel HM, Patil VM, Ansari IA, Ambhore JP, Shinde SD, Kadri A, Snoussi M, Adnan M, Kharkar PS, Pasupuleti VR, Deshmukh PK. Antibiotics 2022; 11: 566
7b Mujahid M, Trendafilova N, Rosair G, Kavanagh K, Walsh M, Creaven BS, Georgieva I. Molecules 2023; 28: 4560

8a Xi G.-L, Liu Z.-Q. J. Agric. Food. Chem. 2015; 63: 3516
8b Chen C, Wang P, Zou LW, Yang L, Fan YM, Hu WZ, Ge GB. Chem. Res. Chin. Univ. 2017; 33: 194

9 Serra S, Chicca A, Delogu G, Vazquez-Rodriguez S, Santana L, Uriarte E, Casu L, Gertsch J. Bioorg. Med. Chem. Lett. 2012; 22: 5791

10a Andrianjafy TM, Ravaomanarivo LH, Ramanandraibe VV, Rakotondramanga MF, Mavingui P, Lemaire M. J. Chem. Ecol. 2018; 44: 299
10b Kischel J, Mertins K, Michalik D, Zapf A, Beller M. Adv. Synth. Catal. 2007; 349: 865
10c Montagut-Romans A, Boulven M, Lemaire M, Popowycz F. New J. Chem. 2014; 38: 1794
10d Rueping M, Nachtsheim BJ, Sugiono E. Synlett 2010; 1549

11a Su Q, Qian H, Li Z, Sun X, Wang Z. Asian J. Org. Chem. 2017; 6: 512
11b Kischel J, Michalik D, Zapf A, Beller M. Chem. Asian J. 2007; 2: 909

12a Koduri ND, Wang Z, Cannell G, Cooley K, Lemma TM, Miao K, Michael N, Frohock B, Castaneda M, Scott H, Albinescu D, Hussaini SR. J. Org. Chem. 2014; 79: 7405
12b Ren X, Liu N, Chandgude AL, Fasan R. Angew. Chem. Int. Ed. 2020; 59: 21634
12c Ren X, Chandgude AL, Fasan R. ACS Catal. 2020; 10: 2308
12d Wang R, He H, Yan Q, Wang W, Wang H, Chen F. J. Flow Chem. 2023; 13: 1
12e Dong K, Liu X.-S, Wei X, Zhao Y, Liu L. Green Synth. Catal. 2021; 2: 385
12f Shi T, Li X, Li Y, Fu X, Wu L, Wu D, Hu W. Green Synth. Catal. 2023; 4: 58
12g Tian X, Xu X, Jing T, Kang Z, Hu W. Green Synth. Catal. 2021; 2: 337
12h Wang H, Sun X, Hu M, Zhang X, Xie L, Gu S. Adv. Synth. Catal. 2020; 362: 3347
12i He H, Yan Z, Wang J, Yan Q, Wang W, Wang H, Chen F. New J. Chem. 2022; 46: 22513

13a Xiang YY, Wang C, Ding QP, Peng YY. Adv. Synth. Catal. 2019; 361: 919
13b Yan ZW, He HL, Yuan DB, Yan QJ, Wang W, Jiang HP, Wang HF, Chen FE. Chem. Commun. 2022; 59: 106
13c He H, Yan J, Jin J, Yan Z, Yan Q, Wang W, Jiang H, Wang H, Chen F. Chem. Commun. 2022; 58: 6429

14 General procedure for the synthesis of oxygen alkylation products: 4-Hydroxycoumarin derivatives 1 (0.10 mmol) and diazo compound 2 (0.3 mmol) in CH₂Cl₂ (1.0 mL) were added to a 10 mL reaction tube. A solution of CF₃SO₃H (0.02 mmol, 20 mol%) in CH₂Cl₂ (1 mL) was then introduced into the reaction mixture. The resulting mixture was continually stirred under a nitrogen atmosphere and heated to reflux for 3–6 h. The reaction solution was concentrated under reduced pressure. The crude product was purified by column chromatography on silica gel to afford pure products 3. Ethyl 2-((2-oxo-2H-chromen-4-yl)oxy)-2-phenylacetate (3a): Prepared by the general procedure. Compound 3a was isolated as a white solid; 84% yield (27.2 mg); eluent: petroleum ether/ethyl acetate = 15:1; mp 140–142 ℃. ¹H NMR (400 MHz, CDCl₃): δ = 7.92 (dd, J = 8.0, 1.6 Hz, 1 H), 7.55–7.46 (m, 3 H), 7.44–7.32 (m, 3 H), 7.29–7.20 (m, 2 H), 5.63 (s, 1 H), 5.54 (s, 1 H), 4.28–4.08 (m, 2 H), 1.18 (t, J = 7.2 Hz, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 167.6, 164.1, 162.4, 153.4, 133.4, 132.7, 129.8, 129.2, 127.1, 124.1, 123.4, 116.8, 115.4, 92.2, 78.9, 62.4, 14.0. HRMS (ESI): m/z [M + H]⁺ calcd for C₁₉H₁₇O₅ ⁺: 325.1071; found: 325.1074. Ethyl 2-(4-chlorophenyl)-2-((2-oxo-2H-chromen-4-yl)oxy)acetate (3f): Prepared by the general procedure. Compound 3f was isolated as a white solid; 81% yield (29.0 mg); eluent: petroleum ether/ethyl acetate = 15:1; mp 102–104 ℃. ¹H NMR (400 MHz, CDCl₃): δ = 7.91–7.85 (m, 1 H), 7.53–7.44 (m, 3 H), 7.38–7.33 (m, 2 H), 7.27–7.21 (m, 2 H), 5.61 (s, 1 H), 5.51 (s, 1 H), 4.25–4.09 (m, 2 H), 1.17 (t, J = 7.2 Hz, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 167.3, 163.9, 162.2, 153.4, 135.9, 132.8, 131.9, 129.4, 128.5, 124.2, 123.3, 116.8, 115.3, 92.3, 78.1, 62.6, 14.0. HRMS (ESI): m/z [M + H]⁺ calcd for C₁₉H₁₆ClO₅ ⁺: 359.0681; found: 359.0686.
15 General procedure for the synthesis of carbon alkylation products: 4-Hydroxycoumarin derivatives 1 (0.10 mmol) and diazo compound 4 (0.3 mmol) in CH₂Cl₂ (1.0 mL) were added to a 10 mL reaction tube. A solution of CF₃SO₃H (0.02 mmol, 20 mol%) in CH₂Cl₂ (1 mL) was then introduced into the reaction mixture. The resulting mixture was continually stirred under a nitrogen atmosphere and heated to reflux for 3–6 h. The reaction solution was concentrated under reduced pressure. The crude product was purified by column chromatography on silica gel to afford the pure products 5. Ethyl 2-(4-hydroxy-2-oxo-2H-chromen-3-yl)-2-(4-(methylthio)phenyl)acetate (5b): Prepared by the general procedure. Compound 5b was isolated as a yellow oil; 65% yield (24.1 mg); eluent: petroleum ether/ethyl acetate = 15:1. ¹H NMR (400 MHz, CDCl₃): δ = 12.08 (s, 1 H), 7.95–7.83 (m, 1 H), 7.50–7.44 (m, 1 H), 7.25–7.18 (m, 4 H), 7.14–7.10 (m, 2 H), 5.59 (s, 1 H), 4.31–4.18 (m, 2 H), 2.36 (s, 3 H), 1.27 (t, J = 7.2 Hz, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 177.8, 163.5, 163.2, 152.6, 138.6, 133.1, 132.5, 127.8, 127.0, 124.1, 124.0, 116.8, 116.3, 100.9, 63.6, 48.3, 15.7, 13.9. HRMS (ESI): m/z [M + H]⁺ calcd for C₂₀H₁₉O₅S⁺: 371.0948; found: 371.0951.

16a Ciszewski LW, Rybicka-Jasinska K, Gryko D. Org. Biomol. Chem. 2019; 17: 432
16b Candeias NR, Paterna R, Gois PM. P. Chem. Rev. 2016; 116: 2937

17a Davies HM. L, Beckwith RE. J. Chem. Rev. 2003; 103: 2861
17b Zhang Z, Wang J. Tetrahedron 2008; 64: 6577
17c Davies HM. L, Denton JR. Chem. Soc. Rev. 2009; 38: 3061
17d Doyle MP, Duffy R, Ratnikov M, Zhou L. Chem. Rev. 2010; 110: 704
17e Ford A, Miel H, Ring A, Slattery CN, Maguire AR, McKervey MA. Chem. Rev. 2015; 115: 9981

Zusatzmaterial

Supporting Information