Nonenzymatic Biomimetic Synthesis of Black Tea Pigment Theaflavins

Yosuke Matsuo; Ryosuke Oowatashi; Yoshinori Saito; Takashi Tanaka

doi:10.1055/s-0036-1588529

Synlett, Inhaltsverzeichnis

Synlett 2017; 28(18): 2505-2508
DOI: 10.1055/s-0036-1588529

letter

Nonenzymatic Biomimetic Synthesis of Black Tea Pigment Theaflavins

Yosuke Matsuo *

Graduate School of Biomedical Sciences, Nagasaki University, 1-14 Bunkyo-machi, Nagasaki 852-8521, Japan eMail: y-matsuo@nagasaki-u.ac.jp eMail: t-tanaka@nagasaki-u.ac.jp

,

Ryosuke Oowatashi

Graduate School of Biomedical Sciences, Nagasaki University, 1-14 Bunkyo-machi, Nagasaki 852-8521, Japan eMail: y-matsuo@nagasaki-u.ac.jp eMail: t-tanaka@nagasaki-u.ac.jp

,

Yoshinori Saito

Graduate School of Biomedical Sciences, Nagasaki University, 1-14 Bunkyo-machi, Nagasaki 852-8521, Japan eMail: y-matsuo@nagasaki-u.ac.jp eMail: t-tanaka@nagasaki-u.ac.jp

,

Takashi Tanaka *

Graduate School of Biomedical Sciences, Nagasaki University, 1-14 Bunkyo-machi, Nagasaki 852-8521, Japan eMail: y-matsuo@nagasaki-u.ac.jp eMail: t-tanaka@nagasaki-u.ac.jp

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Abstract

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Abstract

Theaflavins are reddish-orange black tea pigments with a benzotropolone chromophore, and their various biological activities have been reported. Theaflavins are produced by oxidative coupling between catechol-type and pyrogallol-type catechins via bicyclo[3.2.1]octane-type intermediates. In this study, a new method for nonenzymatic biomimetic synthesis of theaflavins was developed using the DPPH radical as an oxidizing agent.

Key words

theaflavins - quinones - black tea - benzotropolones - bicyclo[3.2.1]octane - biomimetic synthesis

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Referenzen

References and Notes

For reviews of plant polyphenols, see:

1a Crozier A. Jaganath IB. Clifford MN. Nat. Prod. Rep. 2009; 26: 1001
1b Quideau S. Deffieux D. Douat-Casassus C. Pouységu L. Angew. Chem. Int. Ed. 2011; 50: 586
1c Cheynier V. Phytochem. Rev. 2012; 11: 153

2 Engelhardt UH. Chemistry of Tea. In Reference Module in Chemistry, Molecular Sciences and Chemical Engineering. Reedijk J. Elsevier; Waltham, MA: 2013.

For reviews of the chemistry of black tea polyphenols, see:

3a Haslam E. Phytochemistry 2003; 64: 61
3b Drynan JW. Clifford MN. Obuchowicz J. Kuhnert N. Nat. Prod. Rep. 2010; 27: 417
3c Tanaka T. Matsuo Y. Kouno I. Int. J. Mol. Sci. 2010; 11: 14
3d Matsuo Y. Tanaka T. In Recent Advances in Polyphenol Research . Vol. 5. Yoshida K. Cheynier V. Quideau S. Wiley-Blackwell; Chichester: 2017: 67

4a Takino Y. Imagawa H. Horikawa H. Tanaka A. Agric. Biol. Chem. 1964; 28: 64
4b Takino Y. Imagawa H. Agric. Biol. Chem. 1964; 28: 255
4c Takino Y. Ferretti A. Flanagan V. Gianturco M. Vogel M. Tetrahedron Lett. 1965; 6: 4019
4d Collier PD. Bryce T. Mallows R. Thomas PE. Frost DJ. Korver O. Wilkins CK. Tetrahedron 1973; 29: 125

5a Sun L. Warren FJ. Netzel G. Gidley MJ. J. Funct. Foods 2016; 26: 144
5b Hara Y. Honda M. Agric. Biol. Chem. 1990; 54: 1939

6a Matsui T. Tanaka T. Tamura S. Toshima A. Tamaya K. Miyata Y. Tanaka K. Matsumoto K. J. Agric. Food Chem. 2007; 55: 99
6b Honda M. Hara Y. Biosci., Biotechnol., Biochem. 1993; 57: 123

7a Nakai M. Fukui Y. Asami S. Toyoda-Ono Y. Iwashita T. Shibata H. Mitsunaga T. Hashimoto F. Kiso Y. J. Agric. Food Chem. 2005; 53: 4593
7b Kusano R. Andou H. Fujieda M. Tanaka T. Matsuo Y. Kouno I. Chem. Pharm. Bull. 2008; 56: 266

8a Aneja R. Odoms K. Denenberg AG. Wong HR. Crit. Care Med. 2004; 32: 2097
8b Zu M. Yang F. Zhou W. Liu A. Du G. Zheng L. Antiviral Res. 2012; 94: 217

9 Yanase E. Sawaki K. Nakatsuka S. Synlett 2005; 2661

10a Verloop AJ. W. Gruppen H. Bisschop R. Vincken J.-P. Food Chem. 2016; 196: 1197
10b Yabuki C. Yagi K. Nanjo F. Process Biochem. 2017; 55: 61
10c Narai-Kanayama A. Kawashima A. Uchida Y. Kawamura M. Nakayama T. J. Mol. Catal. B: Enzym. 2017;
10d Jhoo J.-W. Sang S. Wei G.-J. Lee TC. Rosen RT. Ho C.-T. J. Food Lipids 2004; 11: 89
10e Lei S. Xie M. Hu B. Zhou L. Sun Y. Saeeduddin M. Zhang H. Zeng X. Int. J. Biol. Macromol. 2017; 94: 709
10f Teng J. Gong Z. Deng Y. Chen L. Li Q. Shao Y. Lin L. Xiao W. LWT – Food Sci. Technol. 2017; 84: 263

11 Sang S. Lambert JD. Tian S. Hong J. Hou Z. Ryu J.-H. Stark RE. Rosen RT. Huang M.-T. Yang CS. Ho C.-T. Bioorg. Med. Chem. 2004; 12: 459

12a Tanaka T. Mine C. Inoue K. Matsuda M. Kouno I. J. Agric. Food Chem. 2002; 50: 2142
12b Van Der Westhuizen M. Steenkamp L. Steenkamp P. Apostolides Z. Biocatal. Biotransform. 2015; 33: 298

13 Takemoto M. Takemoto H. Sakurada A. Tetrahedron Lett. 2014; 55: 5038
14 Yoruk R. Marshall MR. J. Food Biochem. 2003; 27: 361
15 Qi X. Fitoterapia 2010; 81: 205
16 Yanase E. Matsumoto E. Shinoda Y. Nakatsuka S. ITE Lett. Batteries, New Technol. Med. 2005; 6: 232

17a Kawabe Y. Aihara Y. Hirose Y. Sakurada A. Yoshida A. Inai M. Asakawa T. Hamashima Y. Kan T. Synlett 2013; 24: 479
17b Asakawa T. Kawabe Y. Yoshida A. Aihara Y. Manabe T. Hirose Y. Sakurada A. Inai M. Hamashima Y. Furuta T. Wakimoto T. Kan T. J. Antibiot. 2016; 69: 299

18 Sawai Y. Sakata K. J. Agric. Food Chem. 1998; 46: 111

The kinetic and mechanistic studies for the oxidation of catechol derivatives including 5 and 9 by DPPH radical were also reported:

19a Suzuki M. Mori M. Nanjo F. Hara Y. In Caffeinated Beverages, Health Benefits, Physiological Effects, and Chemistry . Parliment TH. Ho CT. Schieberle P. Vol. 754. ACS Symposium Series, American Chemical Society; Washington, DC: 2000: 146
19b Goupy P. Dufour C. Loonis M. Dangles O. J. Agric. Food Chem. 2003; 51: 615
19c Dangles O. Fargeix G. Dufour C. J. Chem. Soc., Perkin Trans. 2 2000; 1653
19d Chen W.-L. Li W.-S. Fu P.-J. Yeh A. Int. J. Chem. Kinet. 2011; 43: 147
19e Lin L.-M. Li W.-S. Chen W.-L. Yeh A. J. Chin. Chem. Soc. 2010; 57: 883

20 Currently, we are investigating the structure of the bicyclo[3.2.1]octane intermediate by converting it into a stable derivative. The details will be reported in the near future.
21 Experimental Procedure for Synthesis of Theaflavin (1) DPPH (543 mg, 1.4 mmol) was added to an acetone solution (100 mL) of epicatechin (5, 200 mg, 0.69 mmol). After stirring for 1 h at r.t., an acetone solution (50 mL) of epigallocatechin (7, 106 mg, 0.35 mmol) was added to the reaction mixture and stirred for 15 min at r.t. Then, water (150 mL) was added to the reaction mixture and stirred for 15 min. The reaction mixture was concentrated in vacuo, and the residue was applied to a column of MCI-gel CHP20P (3.0 × 24 cm; 0–80% aq MeOH, 10% stepwise, each 200 mL) to afford a crude theaflavin (1) fraction along with 5 (154 mg, 77%). The crude fraction of 1 was purified with Sephadex LH-20 (3.0 × 20 cm; 40–100% aq MeOH, 10% stepwise, each 200 mL) to afford 1 ^4c,d,11,22 (91.3 mg, 0.16 mmol, 47% from 7) and theanaphthoquinone (10)²³ (2.9 mg, 0.0054 mmol, 1.6% from 7). Analytical Data for Theaflavin (1) Reddish-orange amorphous powder, [α]_D ²⁵ –234 (c 0.105, MeOH). FAB-MS: m/z = 565 [M + H]⁺, 587 [M + Na]⁺. HRMS–FAB: m/z calcd for C₂₉H₂₅O₁₂: 565.1346; found: 565.1340 [M + H]⁺. IR: 3406, 2935, 1627, 1604, 1518, 1470, 1419, 1310, 1227 cm^–1. UV (MeOH): λ_max (log ε) = 462 (3.49), 378 (3.90), 267 (4.27). ¹H NMR (400 MHz, acetone-d ₆ + D₂O, 95:5): δ = 8.00 (s, H-g), 7.93 (s, H-e), 7.53 (s, H-c), 6.04 (d, J = 2.2 Hz, H-6′), 6.02 (d, J = 2.4 Hz, H-6), 5.99 (d, J = 2.2 Hz, H-8′), 5.95 (d, J = 2.4 Hz, H-8), 5.69 (s, H-2′), 4.98 (s, H-2), 4.45 (m, H-3′), 4.36 (m, H-3), 2.95 (dd, J = 16.8, 4.4 Hz, H-4′a), 2.89 (dd, J = 16.8, 4.4 Hz, H-4a), 2.80 (dd, J = 16.8, 2.3 Hz, H-4b), 2.77 (br d, J = 16.8 Hz, H-4′b). ¹³C NMR (100 MHz, acetone-d ₆ + D₂O, 95:5): δ = 185.1 (C-a), 157.8, 157.7, 157.6, 157.5 (C-5, 7, 5′, 7′), 157.0 (C-8′a), 156.5 (C-8a), 154.6 (C-b), 150.4 (C-i), 146.1 (C-h), 135.0 (C-d), 131.7 (C-f), 128.6 (C-k), 126.9 (C-e), 123.9 (C-g), 121.7 (C-j), 118.9 (C-c), 99.8 (C-4′a), 99.3 (C-4a), 96.5 (2 C, C-6, 6′), 95.6 (C-8′), 95.3 (C-8), 81.2 (C-2), 76.6 (C-2′), 66.2 (C-3), 65.0 (C-3′), 29.5 (C-4′), 29.2 (C-4).

22a Davis AL. Cai Y. Davies AP. Magn. Reson. Chem. 1995; 33: 549
22b Nonaka G. Hashimoto F. Nishioka I. Chem. Pharm. Bull. 1986; 34: 61

23a Tanaka T. Betsumiya Y. Mine C. Kouno I. Chem. Commun. 2000; 1365
23b Jhoo J.-W. Lo C.-Y. Li S. Sang S. Ang CY. W. Heinze TM. Ho C.-T. J. Agric. Food Chem. 2005; 53: 6146

24 Balentine DA. Wiseman SA. Bouwens LC. M. Crit. Rev. Food Sci. Nutr. 1997; 37: 693

25a Bentley R. Nat. Prod. Rep. 2008; 25: 118
25b Liu N. Song W. Schienebeck CM. Zhang M. Tang W. Tetrahedron 2014; 70: 9281

26a Nierenstein M. Swanton A. Biochem. J. 1944; 38: 373
26b Barltrop JA. Nicholson JS. J. Chem. Soc. 1948; 116

27 Arpin N. Favre-Bonvin J. Steglich W. Phytochemistry 1974; 13: 1949
28 Klostermeyer D. Knops L. Sindlinger T. Polborn K. Steglich W. Eur. J. Org. Chem. 2000; 603
29 Kerschensteiner L. Löbermann F. Steglich W. Trauner D. Tetrahedron 2011; 67: 1536

30a Mesa-Siverio D. Estévez-Braun A. Ravelo ÁG. Murguia JR. Rodríguez-Afonso A. Eur. J. Org. Chem. 2003; 4243
30b Fukui N. Ohmori K. Suzuki K. Helv. Chim. Acta 2012; 95: 2194

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