Efficient Synthesis of Several Natural Oligostilbenes from the ­Biomimetic Oxidation of Brominated Isorhapontigenin

Abstract

This study extensively investigated the regioselective oxidative coupling reactions of 5-bromoisorhapontigenin catalyzed by ­FeCl₃·6H₂O or HRP/H₂O₂ in different solvent systems and the distinct reductive debromination of the isolated dimeric coupling intermediates. Natural (±)-bisisorhapontigenin A and (±)-lehmbachol A and B were efficiently prepared. (±)-Gnetuhainin I, (±)-gnemontanin E, (±)-7-O-ethylgnetuhainin I, and (±)-gnemontanin F were synthesized for the first time.

Key words

isorhapontigenin - oligostilbenes - regioselectivity - biomimetic synthesis - oxidative coupling - debromination

• References

• 1a Lin M, Yao CS. Stud. Nat. Prod. Chem. 2006; 33: 601
• 1b Shen T, Wang XN, Lou HX. Nat. Prod. Rep. 2009; 26: 916
• 1c Kawazoe K, Shimogai N, Takaishi Y, Rao KS, Imakura Y. Phytochemistry 1997; 44: 1569
• 1d Zhai Y.-M, Jiang K, Qu S.-J, Luo H.-F, Tan J.-J, Tan C.-H. RSC Adv. 2016; 6: 50083
• 1e Huang K.-S, Wang Y.-H, Li R.-L, Lin M. Phytochemistry 2000; 54: 875

For reviews, see:
• 2a Velu SS, Thomas NF, Weber JF. Curr. Org. Chem. 2012; 16: 605
• 2b Snyder SA, Elsohly AM, Kontes F. Nat. Prod. Rep. 2011; 28: 897
• 2c Synder SA. Recent Adv. Polyphenol Res. 2012; 3: 311
• 2d Li WL, Zang P, Li HF, Yang SX. Prog. Chem. 2012; 24: 545
• 2e Li WL, Lv T, Yang YH, Yang YD. Chin. J. Chem. 2013; 33: 2443
• 2f Keylor MH, Matsurra BS, Stephenson CR. J. Chem. Rev. 2015; 115: 8976
• 3a Li X.-M, Huang K.-S, Lin M, Zhou L.-X. Tetrahedron 2003; 59: 4405
• 3b Yao C.-S, Lin M. Heterocycles 2006; 68: 983
• 4a Zhou LX, Lin M. Chin. Chem. Lett. 2000; 11: 515
• 4b Zhou LX, Lin M. Acta Pharm. Sin. 2000; 35: 669
• 4c Yao CS, Zhou LX, Lin M. Chem. Pharm. Bull. 2004; 52: 238
• 4d Li WL, He KK, Li Y, Hou ZJ. Acta Chim. Sin. 2005; 63: 1607
• 4e Wang X.-F, Zhang Y, Lin M.-B, Yao C.-S, Shi J.-G. J. Asian Nat. Prod. Res. 2014; 16: 511
• 5a Li WL, Luo YL, Li HF, Zang P, Han XQ. Synthesis 2010; 3822
• 5b Li WL, Yang SX, Lv T, Yang YD. Org. Biomol. Chem. 2014; 12: 2273
• 6a Li WL, Dong T, Chen PL, Liu XL, Liu MJ, Han XQ. Tetrahedron 2017; 73: 3056
• 6b Liu MJ, Guan XC, Shao ZB, Li WL. Tetrahedron 2018; 74: 4013