A Facile and Practical Total Synthetic Route for Ampelopsin F and Permethylated ε-Viniferin

Jifa Zhang; Jianqiao Zhang; Yulong Kang; Jiangong Shi; Chunsuo Yao

doi:10.1055/s-0035-1561419

Synlett, Table of Contents

Synlett 2016; 27(10): 1587-1591
DOI: 10.1055/s-0035-1561419

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A Facile and Practical Total Synthetic Route for Ampelopsin F and Permethylated ε-Viniferin

Jifa Zhang

State Key Laboratory of Bioactive Substance and Function of Natural Medicines, Institute of Materia Medica, Chinese Academy of Medical Sciences & Peking Union Medical College, Beijing 100050, P. R. of China Email: yaocs@imm.ac.cn

,

Jianqiao Zhang

State Key Laboratory of Bioactive Substance and Function of Natural Medicines, Institute of Materia Medica, Chinese Academy of Medical Sciences & Peking Union Medical College, Beijing 100050, P. R. of China Email: yaocs@imm.ac.cn

,

Yulong Kang

State Key Laboratory of Bioactive Substance and Function of Natural Medicines, Institute of Materia Medica, Chinese Academy of Medical Sciences & Peking Union Medical College, Beijing 100050, P. R. of China Email: yaocs@imm.ac.cn

,

Jiangong Shi

State Key Laboratory of Bioactive Substance and Function of Natural Medicines, Institute of Materia Medica, Chinese Academy of Medical Sciences & Peking Union Medical College, Beijing 100050, P. R. of China Email: yaocs@imm.ac.cn

,

Chunsuo Yao*

State Key Laboratory of Bioactive Substance and Function of Natural Medicines, Institute of Materia Medica, Chinese Academy of Medical Sciences & Peking Union Medical College, Beijing 100050, P. R. of China Email: yaocs@imm.ac.cn

› Author Affiliations

Abstract

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Abstract

Stilbene dimers (±)-ampelospin F and permethylated (±)-ε-viniferin were synthesized by a practical synthetic route with overall yields of 10% and 27% . This route involves triethylsilane-mediated reduction of the 2,3-diarylbenzofuran,, and BBr₃-mediated one-pot demethylation and cascade intramolecular cyclization reaction.

Key words

total synthesis - ampelopsin F - ε-viniferin - stilbene dimer - BBr₃

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References

References and Notes

1a Ha DT, Chen QC, Hung TM, Youn UJ, Ngoc TM, Thuong PT, Kim HJ, Seong YH, Min BS, Bae KH. Arch. Pharm. Res. 2009; 32: 177
1b Ahmat N, Wibowo A, Mohamad SA. S, Low AL. M, Sufian AS, Yusof M, Latip J. J. Nat. Prod. Res. 2014; 16: 1099
1c Oshima Y, Ueno Y, Hisamichi K, Takeshita M. Tetrahedron 1993; 49: 5801

2a Ha DT, Kim HJ, Thuong PT, Ngoc TM, Lee I, Hung ND, Bae K. J. Ethnopharmacol. 2009; 125: 304
2b Yim N, Trung TN, Kim JP, Lee S, Na M, Jung H, Kim HS, Kim YH, Bae K. Bioorg. Med. Chem. Lett. 2010; 20: 1165

3a Privat C, Telo JP, Bernardes-Genisson V, Vieira A, Souchard JP, Nepveu F. J. Agric. Food Chem. 2002; 50: 1213
3b Schnee S, Queiroz EF, Voinesco F, Marcourt L, Dubuis PH, Wolfender JL, Gindro K. J. Agric. Food Chem. 2013; 61: 5459
3c Yáñez M, Fraiz N, Cano E, Orallo F. Eur. J. Pharmacol. 2006; 542: 54
3d Zghonda N, Yoshida S, Ezaki S, Otake Y, Murakami C, Mliki A, Ghorbel A, Miyazaki H. Biosci. Biotechnol. Biochem. 2012; 76: 954
3e Lin M, Yao CS. Stud. Nat. Prod. Chem. 2006; 33: 601

4a Snyder SA, Zografos AL, Lin Y. Angew. Chem. Int. Ed. 2007; 46: 8186
4b Snyder SA, Breazzano SP, Ross AG, Lin Y, Zografos AL. J. Am. Chem. Soc. 2009; 131: 1753
4c Lindgren AE. G, Öberg CT, Hillgren JM, Elofsson M. Eur. J. Org. Chem. 2016; 426

5a Huang KS, Lin M, Wang YH. Chin. Chem. Lett. 1999; 10: 817
5b Yao CS, Lin M, Wang YH. Chin. J. Chem. 2004; 22: 1350
5c Takaya Y, Terashima K, Ito J, He YH, Tateoka M, Yamaguchi N, Niwa M. Tetrahedron 2005; 61: 10285
5d Wang GW, Wang HL, Capretto DA, Han Q, Hu RB, Yang SD. Tetrahedron 2012; 68: 5216

6 Li W, Li H, Luo Y, Yang Y, Wang N. Synlett 2010; 1247
7 Takaya Y, Yan KX, Terashima K, Ito J, Niwa M. Tetrahedron 2002; 58: 7259
8 Kim I, Choi J. Org. Biomol. Chem. 2009; 7: 2788
9 Wang XF, Yao CS. J. Asian Nat. Prod. Res. 2016; 18 in press; DOI: 10.1080/10286020.2015.1094464
10 Fischer J, Savage GP, Coster MJ. Org. Lett. 2011; 13: 3376

11a Rupprecht KM, Boger J, Hoogsteen K, Nachbar RB, Springer JP. J. Org. Chem. 1991; 56: 6180
11b Lau CK, Belanger PC, Dufresne C, Scheigetz J, Therien M, Fitzsimmons B, Young RN, Ford-Hutchinson AW, Riendeau D, Denis D, Guay J, Charleson S, Piechuta H, McFarlane CS, Chiu S.-HL, Chiu D, Eline RF, Alvaro G, Miwa J, Walsh L. J. Med. Chem. 1992; 35: 1299

12a Lanzilotti AE, Littell R, Fanshawe WJ, Mckenzie TC, Lovell FM. J. Org. Chem. 1979; 44: 4809
12b Kursanov DN, Parnes ZN, Loim NM. Synthesis 1974; 633

13 General Procedure for the Synthesis of Compound 12 t-BuOK (303 mg, 2.73 mmol) was added to a stirred solution of diethyl(4-methoxyphenyl)phosphonate (659 mg, 2.70 mmol) in THF (15 mL) at –40 °C. Then compound 4 (810 mg, 1.93 mmol) in THF (20 mL) was added, and the mixture was stirred at room temperature for 24 h. After the solvent was removed under reduced pressure, the mixture was diluted with EtOAc, washed with brine and water, dried over anhydrous Na₂SO₄, and concentrated in vacuo. The residue was purified by column chromatography over silica gel to afford compound 12. Analytical Data of Compound 12 Yield 98%, colorless oil; [α]_D ²⁵ 0 (c 0.07, MeOH). ¹H NMR (500 MHz, acetone-d ₆): δ = 7.31 (d, J = 8.7 Hz, 2 H), 7.26 (d, J = 8.7 Hz, 2 H), 7.04 (d, J = 16.4 Hz, 1 H), 6.94 (d, J = 8.7 Hz, 2 H), 6.83 (d, J = 8.7 Hz, 2 H), 6.82 (d, J = 2.4 Hz, 1 H), 6.79 (d, J = 16.4 Hz, 1 H), 6.48 (d, J = 2.4 Hz, 2 H), 6.46 (d, J = 2.4 Hz, 1 H), 6.39 (t, J = 2.4 Hz, 1 H), 5.57 (d, J = 5.5 Hz, 1 H), 4.66 (d, J = 5.5 Hz, 1 H), 3.85 (s, 3 H), 3.80 (s, 3 H), 3.77 (s, 3 H), 3.74 (s, 6 H). ¹³C NMR (125 MHz, acetone-d ₆): δ = 162.34 (4 C), 160.61, 160.54, 147.20, 136.26, 134.72, 130.89, 130.23, 128.61 (2 C), 127.87 (2 C), 123.97, 121.03, 114.86 (2 C), 114.79 (2 C), 106.79 (2 C), 102.95, 99.33, 95.77, 93.65, 57.19, 55.84, 55.62 (2 C), 55.57 (2 C). ESI-HRMS: m/z calcd for C₃₃H₃₃O₆Na: 547.2097; found: 547.2103.
14 General Procedure for the Synthesis of Compound 1 To a solution of compound 12 (200 mg, 0.38 mmol) in CH₂Cl₂ (20 mL), a solution of BBr₃ (4.6 mmol) in dichloromethane (20 mL) was added at –50 °C. The mixture was warmed up to –20 °C and stirred for 4 h. After stirred overnight at 5 °C, MeOH (5 mL) was added at –50 °C to quench the reaction. The solution was diluted with EtOAc, washed with water, dried over anhydrous Na₂SO₄, and evaporated under reduced pressure to afford a red residue, which was then purified through silica gel column chromatography and Sephadex LH-20 to afford compound 1. Analytical Cata of Compound 1 Yield 39%, reddish solid, mp 218.5–222.1 °C; [α]_D ²⁵ 0 (c 0.1, MeOH). ¹H NMR (500 MHz, CD₃OD): δ = 7.02 (d, J = 8.5 Hz, 2 H), 6.72 (d, J = 8.5 Hz, 2 H), 6.69 (d, J = 8.5 Hz, 2 H), 6.51 (d, J = 8.6 Hz, 2 H), 6.38 (d, J = 2.0 Hz, 1 H), 6.36 (d, J = 2.4 Hz, 1 H), 6.08 (d, J = 2.4 Hz, 1 H), 6.01 (d, J = 2.0 Hz, 1 H), 4.09 (d, J = 1.5 Hz, 1 H), 4.03 (s, 1 H), 3.56 (s, 1 H), 3.23 (s, 1 H). ¹³C NMR (125 MHz, CD₃OD): δ = 158.48 (s), 158.08 (s), 157.12 (s), 156.13, 156.11, 153.16 (s), 147.85 (s), 147.53 (s), 139.07 (s), 136.09 (s), 130.08 (2 C), 129.37 (2 C), 128.72 (s), 115.76 (2 C), 115.59 (2 C), 114.11 (s), 105.78, 104.32, 102.01, 101.92, 59.28, 50.95, 49.85, 47.65. ESI-HRMS: m/z calcd for C₂₈H₂₁O₆: 453.1338; found: 453.1351 [M – H]^–.

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