An Efficient Strategy for Protecting Dihydroxyl Groups of Catechols

Wei-Bin Huang; Ying Guo; Jian-An Jiang; Xian-Dao Pan; Dao-Hua Liao; Ya-Fei Ji

doi:10.1055/s-0032-1318332

Synlett, Table of Contents

Synlett 2013; 24(6): 741-746
DOI: 10.1055/s-0032-1318332

letter

An Efficient Strategy for Protecting Dihydroxyl Groups of Catechols

Authors

Wei-Bin Huang

^aSchool of Pharmacy, East China University of Science & Technology, Campus P. O. Box 363, 130 Meilong Road, Shanghai 200237, P. R. of China Fax: +86(21)64253314 Email: jyf@ecust.edu.cn
Ying Guo

^aSchool of Pharmacy, East China University of Science & Technology, Campus P. O. Box 363, 130 Meilong Road, Shanghai 200237, P. R. of China Fax: +86(21)64253314 Email: jyf@ecust.edu.cn
Jian-An Jiang

^aSchool of Pharmacy, East China University of Science & Technology, Campus P. O. Box 363, 130 Meilong Road, Shanghai 200237, P. R. of China Fax: +86(21)64253314 Email: jyf@ecust.edu.cn
Xian-Dao Pan

^bInstitute of Meteria Medica, Chinese Academy of Medical Sciences & Peking Union Medical College, 1 Xiannongtan Street, Beijing 100050, P. R. of China
Dao-Hua Liao

^aSchool of Pharmacy, East China University of Science & Technology, Campus P. O. Box 363, 130 Meilong Road, Shanghai 200237, P. R. of China Fax: +86(21)64253314 Email: jyf@ecust.edu.cn
Ya-Fei Ji*

^aSchool of Pharmacy, East China University of Science & Technology, Campus P. O. Box 363, 130 Meilong Road, Shanghai 200237, P. R. of China Fax: +86(21)64253314 Email: jyf@ecust.edu.cn

Abstract

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Abstract

A novel strategy for protecting dihydroxyl groups of catechols has been developed. Base-mediated cyclizations of catechols with 1,3-dibromopropane provided the corresponding benzo[b]1,4-dioxepans, and herefrom the protecting group was easily cleaved by aluminum chloride. The preparation of the antibacterial and antifungal agent 4-(2-aminothiazol-4-yl)benzene-1,2-diol from catechol reliably verified its availability amenable to various harsh reaction conditions.

Key words

catechols - protection - ortho-dihydroxyl - 1,3-dibromopropane - benzo[b]1,4-dioxepans - deprotection - aluminum chloride

Full Text

References

References and Notes

1a Reinhold DF, Firestone RA, Gaines WA, Chemerda JM, Sletzinger M. J. Org. Chem. 1968; 33: 1209
1b Chang Y.-A, Ares J, Anderson K, Sabol B, Wallace RA, Farooqui T, Uretsky N, Miller DD. J. Med. Chem. 1987; 30: 214
1c Bevan S, Hothi S, Hughes G, James IF, Rang HP, Shah K, Walpole CS, Yeats JC. Br. J. Pharmacol. 1992; 107: 544
1d Rietjens SJ, Bast A, Haenen GR. M. M. J. Agric. Food Chem. 2007; 55: 7609
1e Dalence-Guzman MF, Berglund M, Skogvall S, Sterner O. Bioorg. Med. Chem. 2008; 16: 2499
1f Hao W, Hu Y, Niu C, Huang X, Chang C.-PB, Gibbons J, Xu J. Bioorg. Med. Chem. Lett. 2008; 18: 4988
1g Wang W.-L, Chai SC, Huang M, He H.-Z, Hurley TD, Ye Q.-Z. J. Med. Chem. 2008; 51: 6110

2 Smith RV, Velagapudi RB, McLean AM, Wilcox RE. J. Med. Chem. 1985; 28: 613
3 Liedhegner EA. S, Steller KM, Mieyal JJ. Chem. Res. Toxicol. 2011; 24: 1644
4 Guay DR. P. Pharmacotherapy 1999; 19: 6
5 Holm KJ, Spencer CM. Drugs 1999; 58: 159
6 Fitton A, Benfield P. Drugs 1990; 39: 308
7 O’Donnell J, Zeppenfeld D, McConnell E, Pena S, Nedergaard M. Neurochem. Res. 2012; 37: 2496

8a DeBernardis JF, Arendsen DL, Kyncl JJ, Kerkman DJ. J. Med. Chem. 1987; 30: 178
8b Sit S.-Y, Xie K, Jacutin-Porte S, Taber MT, Gulwadi AG, Korpinen CD, Burris KD, Molski TF, Ryan E, Xu C, Wong H, Zhu J, Krishnananthan S, Gao Q, Verdoorn T, Johnson G. J. Med. Chem. 2002; 45: 3660

9a Kawase M, Sinhababu AK, McGhee EM, Milby T, Borchardt RT. J. Med. Chem. 1990; 33: 2204
9b O’Malley SJ, Tan KL, Watzke A, Bergman RG, Ellman JA. J. Am. Chem. Soc. 2005; 127: 13496

10a Cabezon B, Quesada E, Esperanza S, Torres T. Eur. J. Org. Chem. 2000; 2767
10b Madrona A, Pereira-Caro G, Mateos R, Rodriguez G, Trujillo M, Fernandez-Bolanos J, Espartero JL. Molecules 2009; 14: 1762

11a Gambacorta A, Tofani D, Bernini R, Migliorini A. J. Agric. Food Chem. 2007; 55: 3386
11b Bernini R, Crisante F, Merendino N, Molinari R, Soldatelli MC, Velotti F. Eur. J. Med. Chem. 2011; 46: 439

12 Alig L, Alsenz J, Andjelkovic M, Bendels S, Benardeau A, Bleicher K, Bourson A, David-Pierson P, Guba W, Hildbrand S, Kube D, Lubbers T, Mayweg AV, Narquizian R, Neidhart W, Nettekoven M, Plancher J.-M, Rocha C, Rogers-Evans M, Rover S, Schneider G, Taylor S, Waldmeier P. J. Med. Chem. 2008; 51: 2115

13a Nicolaou KC, Wang J, Tang Y. Angew. Chem. Int. Ed. 2008; 47: 1432
13b Allais F, Martinet S, Ducrot P.-H. Synthesis 2009; 3571

14 Ariza X, Pineda O, Vilarrasa J, Shipps GW, Ma Y, Dai X. Org. Lett. 2001; 3: 1399
15 Kaupp G, Naimi-Jamal MR, Stepanenko V. Chem. Eur. J. 2003; 9: 4156

16a Mills SJ, Komander D, Trusselle MN, Safrany ST, van Aalten DM. F, Potter BV. L. ACS Chem. Biol. 2007; 2: 242
16b Mills SJ, Vandeput F, Trusselle MN, Safrany ST, Erneux C, Potter BV. L. ChemBioChem 2008; 9: 1757
16c Prasain K, Nguyen TD. T, Gorman MJ, Barrigan LM, Peng Z, Kanost MR, Syed LU, Li J, Zhu KY, Hua DH. Bioorg. Med. Chem. 2012; 20: 1679

17a Chen J, Yang F, Ji G.-Z, Yang H, Shen Z.-W, Zhou X.-J. Langmuir 2005; 21: 10931
17b Pak JJ, Mayo JL, Shurdha E. Tetrahedron Lett. 2006; 47: 233

18 Bernini R, Cacchi S, Fabrizi G, Filisti E. Org. Lett. 2008; 10: 3457

19a Mills SJ, Dozol H, Vandeput F, Backers K, Woodman T, Erneux C, Spiess B, Potter BV. L. ChemBioChem 2006; 7: 1696
19b Cacciarini M, Cordiano E, Nativi C, Roelens S. J. Org. Chem. 2007; 72: 3933
19c Percec V, Imam MR, Peterca M, Leowanawat P. J. Am. Chem. Soc. 2012; 134: 4408

20 Narayana B, Raj KK. V, Ashalatha BV. Phosphorus, Sulfur Silicon Relat. Elem. 2006; 181: 1381

21a Gillespie JP, Amoros LG, Stermitz FR. J. Org. Chem. 1974; 39: 3239
21b Banwell MG, Flynn BL, Stewart SG. J. Org. Chem. 1998; 63: 9139
21c Bushby RJ, Lu Z. Synthesis 2001; 763

22 Huang W.-B, Du C.-Y, Jiang J.-A, Ji Y.-F. Res. Chem. Intermed. 2012; 38 in press; DOI: 10.1007/s11164-012-0804-6
23 Malecha JW, Noble SA, Wiley BM, Hoffman TZ, Bonnefous C, Sertic M, Wash PL, Smith ND, Hassig CA, Scranton SA, Payne JE, Hager J. US 2007/0027184A1, 2007 ; Chem. Abstr. 2007, 146, 206220
24 General Cyclization Procedure To EtOH (15 mL) were added in turn catechols 1 (5.0 mmol), K₂CO₃ (2.42 g, 17.5 mmol) and 1,3-dibromopropane (0.66 mL, 6.5 mmol), then the mixture was heated at reflux for 5 h. The resulting mixture was filtered and concentrated to acquire the crude product, the purification of which by column chromatography afforded the corresponding product 2 with PE–EtOAc (30:1, v/v) as eluents. Representative Compound 2a Colorless liquid, 0.69 g (92% yield). ¹H NMR (400 MHz, CDCl₃): δ = 2.19 (quint, J = 5.6 Hz, 2 H, CH₂), 4.22 (t, J = 5.6 Hz, 4 H, CH₂), 6.90–6.95 (m, 2 H, Ar), 6.96–7.01 (m, 2 H, Ar) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 31.9, 70.5 (2 C), 121.6 (2 C), 123.3 (2 C), 151.2 (2 C) ppm. ESI-HRMS: m/z [M + H⁺] calcd for C₉H₁₁O₂: 151.0759; found: 151.0757
25 General Deprotection Procedure A solution of benzo[b]1,4-dioxepans 2 (3.0 mmol) in benzene (10 mL) was treated by anhyd AlCl₃ (1.20 g, 9.0 mmol), and the mixture was heated to reflux for specified time. Then, the reaction mixture was quenched by sat. aq NH₄Cl (20 mL), and the aqueous phase was extracted with EtOAc (3 × 10 mL). The combined organic phase was washed by sat. brine (2 × 20 mL) and concentrated to provide the crude product, the purification of which by column chromatography afforded the corresponding product 1 with PE–EtOAc (10:1, v/v) as eluents.
26 Olah GA, Prakash GK. S, Iyer PS, Tashiro M, Yamato T. J. Org. Chem. 1987; 52: 1881
27 Synthetic Procedures for Compounds 4–6 Compound 4 Bromine (0.17 mL, 3.4 mmol, dissolved in 2 mL EtOH) was added dropwise to a stirred solution of 3 (0.50 g, 2.6 mmol) in EtOH (8 mL), and the mixture was stirred at r.t. for 1 h. Then, the solvent was removed to get the crude product, the purification of which by column chromatography afforded the pure product 4 with PE–CH₂Cl₂ (15:1, v/v) as eluents; white solid; mp 72–74 °C; 0.62 g (88% yield). ¹H NMR (400 MHz, CDCl₃): δ = 2.25 (quint, J = 5.6 Hz, 2 H, CH₂), 4.28 (t, J = 5.6 Hz, 2 H, CH₂), 4.34 (t, J = 5.6 Hz, 2 H, CH₂), 4.37 (s, 2 H, CH₂), 7.00 (d, J = 8.4 Hz, 1 H, Ar), 7.57 (d, J = 8.4 Hz, 1 H, Ar), 7.60 (s, 1 H, Ar) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 30.79, 30.81, 70.2, 70.4, 121.6, 122.7, 124.7, 129.1, 150.6, 156.0, 189.8 ppm. ESI-HRMS: m/z [M + H⁺] calcd for C₁₁H₁₂O₃Br: 270.9970; found: 270.9975. Compound 5 A solution of 4 (0.54 g, 2.0 mmol) and thiourea (0.18 g, 2.4 mmol) in absolute EtOH (12 mL) was refluxed for 2 h. After removal of the solvent, the residue was treated with aq NaOH (1 mol/L, 10 mL), and extracted with EtOAc (3 × 10 mL). The combined organic phase was concentrated to provide the crude product, the purification of which by column chromatography afforded the pure product 5 with PE–EtOAc (4:1, v/v) as eluents; light yellow solid; mp 174–177 °C, 0.46 g (92% yield). ¹H NMR (400 MHz, CDCl₃): δ = 2.20 (quint, J = 5.2 Hz, 2 H, CH₂), 4.22 (t, J = 5.2 Hz, 4 H, CH₂), 5.05 (s, 2 H, NH₂), 6.60 (s, 1 H, thiazole), 6.97 (d, J = 8.4 Hz, 1 H, Ar), 7.34 (d, J = 8.4 Hz, 1 H, Ar), 7.40 (s, 1 H, Ar) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 31.8, 70.6 (2 C), 102.1, 119.3, 121.1, 121.7, 130.3, 150.5, 151.0, 151.2, 167.1. ESI-HRMS: m/z [M + H⁺] calcd for C₁₂H₁₃N₂O₂S: 249.0698; found: 209.0693. Compound 6 A solution of 5 (0.40 g, 1.6 mmol) in benzene (8 mL) was treated by anhyd AlCl₃ (0.64 g, 4.8 mmol), and the mixture was heated to reflux for 10 h. Then, the mixture was quenched by sat. aq NH₄Cl (20 mL). Then aq NaOH (1 mol/L) was added to keep pH 7. The aqueous phase was extracted with EtOAc (3 × 20 mL). The combined organic phase was washed by sat. brine (2 × 20 mL), and then concentrated to provide the crude product, the purification of which by column chromatography afforded the pure product 6 with PE–EtOAc (2:1, v/v) as eluents; yellow solid; mp 228–231 °C; 0.28 g (84% yield). ¹H NMR (400 MHz, DMSO-d ₆): δ = 6.64 (s, 1 H, thiazole), 6.69 (d, J = 8.0 Hz, 1 H, Ar), 6.92 (s, 2 H, OH), 7.06 (dd, J ₁ = 8.0 Hz, J ₂ = 2.0 Hz, 1 H, Ar), 7.19 (d, J = 2.0 Hz, 1 H, Ar), 8.90 (s, 2 H, NH₂) ppm. ¹³C NMR (100 MHz, DMSO-d ₆): δ = 98.3, 113.3, 115.4, 116.9, 126.8, 144.8, 144.9, 150.3, 167.7 ppm. ESI-HRMS: m/z [M + H⁺] calcd for C₉H₉N₂O₂S: 209.0385; found: 209.0381.

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