Selective Synthesis of Epicatechin Dimers By Zinc(II) Triflate Mediated Self-Condensation

Abstract

Epicatechin dimers were synthesized by zinc(II) triflate mediated self-condensation reactions of epicatechin monomer derivatives. One synthesized dimer was successfully converted into procyanidin C1.

Key words

phenols - Lewis acids - oligomerization - natural products - stereoselective synthesis

• References

• 1 Ferreira D, Li X.-C. Nat. Prod. Rep. 2000; 17: 193
• 2 Ferreira D, Slade D. Nat. Prod. Rep. 2002; 19: 517
• 3 Seeram N, Aviram M, Zhang Y, Hennings SM, Feng L, Dreher M, Heber D. J. Agric. Food Chem. 2008; 56: 1415
• 4 Kozikowski AP, Túckmantel W, Böttcher G, Romanczyk LJ. Jr. J. Org. Chem. 2003; 68: 1641
• 5 Mitsuhashi S, Saito A, Nakajima N, Shima H, Ubukata M. Molecules 2008; 13: 2998
• 6 Cheng HY, Lin TC, Yang CM, Shieh DC, Lin CC. J. Sci. Food. Agric. 2005; 85: 10
• 7 Terra X, Valls J, Vitrac X, Merrillon JM, Arola L, Ardevol A, Blade C, Fernandez-Larrea J, Pujadas G, Salvado J, Blay M. J. Agric. Food Chem. 2007; 55: 4357
• 8 Saito A, Emoto M, Tanaka A, Doi Y, Shoji K, Mizushina Y, Ikawa H, Yoshida H, Matsuura N, Nakajima N. Tetrahedron 2004; 60: 12043

For recent reviews on the synthesis of proanthocyanidins, see:
• 9a Makabe H. Heterocycles 2013; 87: 2225
• 9b Ferreira D, Coleman CM. Planta Med. 2011; 77: 1071
• 9c Oyama K, Yoshida K, Kondo T. Curr. Org. Chem. 2011; 15: 2567
• 9d Ohmori K, Suzuki K. Curr. Org. Chem. 2012; 16: 566

For recent syntheses of procyanidin dimers, see:
• 10a Ishihara S, Doi S, Harui K, Okamoto T, Okamoto S, Uenishi J, Kawasaki T, Nakajima N, Saito A. Heterocycles 2014; 88: 1595
• 10b Nakajima N, Horikawa K, Takekawa N, Hamada M, Kishimoto T. Heterocycles 2012; 84: 349
• 10c Katoh M, Oizumi Y, Mohri Y, Hirota M, Makabe H. Lett. Org. Chem. 2012; 9: 233
• 10d Alharthy RD, Hayes CJ. Tetrahedron Lett. 2010; 51: 1193
• 10e Oizumi Y, Mohri Y, Hirota M, Makabe H. J. Org. Chem. 2010; 75: 4884
• 10f Mohri Y, Sagehashi M, Yamada T, Hattori Y, Morimura K, Hamauzu Y, Kamo T, Hirota M, Makabe H. Heterocycles 2009; 79: 549
• 10g Oyama K.-i, Kuwano M, Ito M, Yoshida K, Kondo T. Tetrahedron Lett. 2008; 49: 3176
• 10h Viton F, Landreau C, Rustidge D, Robert F, Williamson G, Barron G. Eur. J. Org. Chem. 2008; 6069
• 10i Mohri Y, Sagehashi M, Yamada T, Hattori Y, Morimura K, Kamo T, Hirota M, Makabe H. Tetrahedron Lett. 2007; 48: 5891
• 10j Tarascou I, Barathieu K, André Y, Pianet I, Dufourc EJ, Fouquet E. Eur. J. Org. Chem. 2006; 5367
• 10k Saito A, Nakajima N, Matsuura N, Tanaka A, Ubukata M. Heterocycles 2004; 62: 479
• 10l Saito A, Nakajima N, Tanaka A, Ubukata M. Heterocycles 2003; 61: 287
• 10m Saito A, Nakajima N, Tanaka A, Ubukata M. Tetrahedron 2002; 58: 7829

For recent syntheses of procyanidin trimers and related compounds, see:
• 11a Yano T, Ohmori K, Takahashi H, Kusumi T, Suzuki K. Org. Biomol. Chem. 2012; 10: 7685
• 11b Oizumi Y, Katoh M, Hattori Y, Toda K, Kawaguchi K, Fujii H, Makabe H. Heterocycles 2012; 85: 2241
• 11c Oizumi Y, Mohri Y, Hattori Y, Makabe H. Heterocycles 2011; 83: 739
• 11d Ohmori K, Ushimaru N, Suzuki K. Proc. Natl. Acad. Sci. U.S.A. 2004; 101: 12002
• 11e Saito A, Doi Y, Tanaka A, Matsuura N, Ubukata M, Nakajima N. Bioorg. Med. Chem. 2004; 12: 4783
• 11f Saito A, Tanaka A, Ubukata M, Nakajima N. Synlett 2004; 1069

For syntheses of procyanidin oligomers, see:
• 12a Ohmori K, Shono T, Hatakoshi Y, Yano T, Suzuki K. Angew. Chem. Int. Ed. 2011; 50: 4862
• 12b Saito A, Mizushina Y, Tanaka A, Nakajima N. Tetrahedron 2009; 65: 7422
• 13 Fujii W, Toda K, Matsumoto K, Kawaguchi K, Kawahara S.-i, Hattori Y, Fujii H, Makabe H. Tetrahedron Lett. 2013; 54: 7188
• 14 HPLC measurement conditions: 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, λ = 280 nm; retention time: 23.60 min.