Synthesis 2016; 48(10): 1525-1532
DOI: 10.1055/s-0035-1561390
paper
© Georg Thieme Verlag Stuttgart · New York

Concise Synthesis of Cinnamtannin A2 from Dimeric Epicatechin Electrophile and Nucleophile Prepared by Zn(OTf)2-Mediated Self-Condensation

Mikihiro Ichikawa ◊
a   Graduate School of Agriculture, Sciences of Functional Foods, Shinshu University, 8304 Minami-minowa, Kami-ina, Nagano, 399-4598, Japan
,
Kohki Takanashi ◊
a   Graduate School of Agriculture, Sciences of Functional Foods, Shinshu University, 8304 Minami-minowa, Kami-ina, Nagano, 399-4598, Japan
,
Manato Suda ◊
a   Graduate School of Agriculture, Sciences of Functional Foods, Shinshu University, 8304 Minami-minowa, Kami-ina, Nagano, 399-4598, Japan
,
Yasunao Hattori
b   Department of Medicinal Chemistry, Kyoto Pharmaceutical University, Yamashina-ku, Kyoto 607-8412, Japan
,
Sei-ichi Kawahara
c   St. Cousair Co., Ltd., 1260 Imogawa, Kami-minochi, Iizuna, Nagano, 389-1201, Japan
,
Hiroshi Fujii
d   Department of Interdisciplinary Genome Sciences and Cell Metabolism, Institute for Biomedical Sciences, Interdisciplinary Cluster for Cutting Edge Research, Shinshu University, Minami-minowa, Kami-ina, Nagano, 399-4598, Japan   Email: makabeh@shinshu-u.ac.jp
,
Hidefumi Makabe*
a   Graduate School of Agriculture, Sciences of Functional Foods, Shinshu University, 8304 Minami-minowa, Kami-ina, Nagano, 399-4598, Japan
d   Department of Interdisciplinary Genome Sciences and Cell Metabolism, Institute for Biomedical Sciences, Interdisciplinary Cluster for Cutting Edge Research, Shinshu University, Minami-minowa, Kami-ina, Nagano, 399-4598, Japan   Email: makabeh@shinshu-u.ac.jp
› Author Affiliations
Further Information

Publication History

Received: 04 January 2016

Accepted after revision: 23 January 2016

Publication Date:
25 February 2016 (online)


◊ These authors contributed equally

Abstract

The synthesis of cinnamtannin A2 from dimeric epicatechin nucleophile and electrophile was accomplished. Dimeric epicatechin nucleophile was prepared directly by reduction of the C-4′′ 1-ethoxy­ethoxy group of the electrophile which was previously synthesized by us.

Supporting Information

 
  • References

    • 1a Esatbeyoglu T, Wray V, Winterhalter P. Food Chem. 2015; 179: 278
    • 1b Natsume M, Osakabe N, Yamagishi M, Takizawa T, Nakamura T, Miyatake H, Hatano T, Yoshida T. Biosci. Biotechnol. Biochem. 2000; 64: 2581
  • 2 Ito C, Oki T, Nanba T, Yamada F, Yamada K, Toda T. Food Chem. 2013; 141: 2507
  • 3 Saito A, Mizushina Y, Tanaka A, Nakajima N. Tetrahedron 2009; 65: 7422
  • 4 Shahat AA, Cos P, De Bruyne T, Apers S, Hammouda FM, Ismail SI, Azzam S, Claeys M, Goovaerts E, Pieters L. Planta Med. 2002; 68: 539
  • 5 Takechi M, Tanaka Y, Takehara M, Nonaka G, Nishioka I. Phytochemistry 1985; 24: 2245
  • 6 Kurimoto Y, Shibayama Y, Inoue S, Soga M, Takikawa M, Ito M, Nanba C, Yoshida F, Ashida H. J. Agric. Food Chem. 2013; 61: 5558
  • 7 Kozikowski AP, Túckmantel W, Böttcher G, Romanczyk LJ. Jr. J. Org. Chem. 2003; 68: 1641
  • 8 Yoneda S, Kawamoto H, Nakatsubo F. J. Chem. Soc., Perkin Trans. 1 1997; 1025
  • 9 Ohmori K, Shono T, Hatakoshi Y, Yano T, Suzuki K. Angew. Chem. Int. Ed. 2011; 50: 4862

    • Recent review of the synthesis of proanthocyanidins:
    • 10a Makabe H. Heterocycles 2013; 87: 2225
    • 10b Ferreira D, Coleman CM. Planta Med. 2011; 77: 1071
    • 10c Oyama K, Yoshida K, Kondo T. Curr. Org. Chem. 2011; 15: 2567
    • 10d Ohmori K, Suzuki K. Curr. Org. Chem. 2012; 16: 566

      Recent syntheses of procyanidin dimers:
    • 11a Fabre S, Gueroux M, Nunes E, Szlosek-Pinaud M, Pianet I. Tetrahedron 2015; 71: 3045
    • 11b Ishihara S, Doi S, Harui K, Okamoto T, Okamoto S, Uenishi J, Kawasaki T, Nakajima N, Saito A. Heterocycles 2014; 88: 1595
    • 11c Nakajima N, Horikawa K, Takekawa N, Hamada M, Kishimoto T. Heterocycles 2012; 84: 349
    • 11d Katoh M, Oizumi Y, Mohri Y, Hirota M, Makabe H. Lett. Org. Chem. 2012; 9: 233
    • 11e Alharthy RD, Hayes CJ. Tetrahedron Lett. 2010; 51: 1193
    • 11f Oizumi Y, Mohri Y, Hirota M, Makabe H. J. Org. Chem. 2010; 75: 4884
    • 11g Mohri Y, Sagehashi M, Yamada T, Hattori Y, Morimura K, Hamauzu Y, Kamo T, Hirota M, Makabe H. Heterocycles 2009; 79: 549
    • 11h Oyama K.-i, Kuwano M, Ito M, Yoshida K, Kondo T. Tetrahedron Lett. 2008; 49: 3176
    • 11i Viton F, Landreau C, Rustidge D, Robert F, Williamson G, Barron G. Eur. J. Org. Chem. 2008; 6069
    • 11j Mohri Y, Sagehashi M, Yamada T, Hattori Y, Morimura K, Kamo T, Hirota M, Makabe H. Tetrahedron Lett. 2007; 48: 5891
    • 11k Tarascou I, Barathieu K, André Y, Pianet I, Dufourc EJ, Fouquet E. Eur. J. Org. Chem. 2006; 5367
    • 11l Saito A, Nakajima N, Matsuura N, Tanaka A, Ubukata M. Heterocycles 2004; 62: 479
    • 11m Saito A, Nakajima N, Tanaka A, Ubukata M. Heterocycles 2003; 61: 287
    • 11n Saito A, Nakajima N, Tanaka A, Ubukata M. Tetrahedron 2002; 58: 7829

      Recent syntheses of procyanidin trimers and related compounds:
    • 12a Yano T, Ohmori K, Takahashi H, Kusumi T, Suzuki K. Org. Biomol. Chem. 2012; 10: 7685
    • 12b Oizumi Y, Katoh M, Hattori Y, Toda K, Kawaguchi K, Fujii H, Makabe H. Heterocycles 2012; 85: 2241
    • 12c Oizumi Y, Mohri Y, Hattori Y, Makabe H. Heterocycles 2011; 83: 739
    • 12d Ohmori K, Ushimaru N, Suzuki K. Proc. Natl. Acad. Sci. U.S.A. 2004; 101: 12002
    • 12e Saito A, Doi Y, Tanaka A, Matsuura N, Ubukata M, Nakajima N. Bioorg. Med. Chem. 2004; 12: 4783
    • 12f Saito A, Tanaka A, Ubukata M, Nakajima N. Synlett 2004; 1069
  • 13 Suda M, Fujii W, Takanashi K, Hattori Y, Makabe H. Synthesis 2014; 46: 3351
  • 14 Suda M, Takanashi K, Katoh M, Matsumoto K, Kawaguchi K, Kawahara S, Fujii H, Makabe H. Nat. Prod. Commun. 2015; 10: 959
  • 15 Cinnamtannin A2: HPLC (column; Inertsil ODS-3 250 × 4.6 mm GL-Sciences, eluent MeOH/0.2% AcOH (5:95 to 25:75), flow rate: 0.8 mL/min, detection: UV 280 nm): t R = 25.10 min.