Concise Total Synthesis of Biologically Interesting Pyranochalcone Natural Products: Citrunobin, Boesenbergin A, Boesenbergin B, Xanthohumol C, and Glabrachromene

Abstract

New and efficient synthetic approaches to the biologically interesting natural products citrunobin, boesenbergins A and B, xanthohumol C, and glabrachromene are described. The key strategies involve ethylenediamine diacetate catalyzed benzopyran formation reactions and base-catalyzed aldol reactions.

Key words

pyranochalcone - citrunobin - boesenbergins A and B - xanthohumol C - glabrachromene

References

• 1a Wagner H. Farkas L. In The Flavonoids   Harborne JB. Mabry TJ. Mabry H. Academic Press; New York: 1975.  p.127 
• 1b Gripenberg J. In The Chemistry of Flavonoid Compounds   Geissman TA. Macmillan; New York: 1962.  p.409 
• 1c Wollenweber E. In The Flavonoids   Harborne JB. Chapman & Hall; London: 1994.  p.259 
• 1d The Handbook of Natural Products   Vol. 2:  Harborne JB. Baxter H. Wiley & Sons; London: 1999.  p.1 
• 1e Fang N. Casida JE. J. Nat. Prod.  1999,  62:  205 
• 1f Saini TR. Pathak VP. Khanna RN. J. Nat. Prod.  1983,  46:  936 
• 1g Pathak VP. Saini TR. Khanna RN. Phytochemistry  1983,  22:  1303 
• 1h Subrahmanyam K. Madhusudhana Rao V. Jagannadha Rao KV. Indian J. Chem., Sect. B: Org. Chem. Incl. Med. Chem.  1977,  15:  12 
• 2a Welton AF. Tobias LD. Fiedler-Nagy C. Anderson W. Hope W. Meyers K. Coffey JW. In Plant Flavonoids in Biology and Medicine: Biochemical, Pharmacological and Structure-Activity Relationships   Cody V. Middleton E. Harborne J. B. Alan R. Liss, Inc.; New York: 1986.  p.231 
• 2b Miranda CL. Stevens JF. Helmrich A. Henderson MC. Rodriguez RJ. Yang Y.-H. Deinzer ML. Barnes DW. Buhler DR. Food Chem. Toxicol.  1999,  37:  271 
• 2c Han A.-R. Kang Y.-J. Windono T. Lee SK. Seo E.-K. J. Nat. Prod.  2006,  69:  719 
• 2d Demizu S. Kajiyama K. Hiraga Y. Kinoshida T. Koyama K. Takahashi K. Tamura Y. Okada K. Kinoshida T. Chem. Pharm. Bull.  1992,  40:  392 
• 3 Shung WT. Phytochemistry  1989,  28:  3558 
• 4a Jaipetch T. Kanghae S. Pancharoen O. Patrick VA. Reutrakul V. Tuntiwachwuttikul P. White AH. Aust. J. Chem.  1982,  35:  351 
• 4b Mahidol C. Tuntiwachwuttikul P. Reutrakul V. Taylor WC. Aust. J. Chem.  1984,  37:  1739 
• 5a Stevens JF. Taylor AW. Nickerson GB. Ivancic M. Henning J. Haunold A. Deinzer ML. Phytochemistry  2000,  53:  759 
• 5b Stevens JF. Ivancic M. Hsu VL. Deinzer ML. Phytochemistry  1997,  44:  1575 
• 6a Gerhäuser C. Alt A. Heiss E. Gamal-Eldeen A. Klimo K. Knauft J. Neumann I. Scherf H.-R. Frank N. Bartsch H. Becker H. Mol. Cancer Ther.  2002,  1:  959 
• 6b Henderson MC. Miranda CL. Stevens JF. Deinzer ML. Buhler DR. Xenobiotica  2000,  30:  235 
• 6c Miranda CL. Aponso GLM. Stevens JF. Deinzer ML. Buhler DR. Cancer Lett.  2000,  149:  21 
• 6d Miranda CL. Stevens JF. Ivanov V. McCall M. Frei B. Deinzer ML. Buhler DR. J. Agric. Food Chem.  2000,  48:  3876 
• 6e Stevens JF. Miranda CL. Frei B. Buhler DR. Chem. Res. Toxicol.  2003,  16:  1277 
• 6f Nikolic D. Li Y. Chadwick LR. Pauli GF. van Breemen RB. J. Mass Spectrom.  2005,  40:  289 
• 7 Mahey S. Sharma P. Seshadri TR. Mukerjee SK. Indian J. Chem.  1972,  10:  585 
• 8 Subramanian M. Kumaraswami K. Rajendra Prasad KJ. J. Nat. Prod.  1992,  55:  1213 
• 9 Lee YR. Kim DH. Synthesis  2006,  603 
• 10a Bogaert-Alvarez RJ. Demena P. Kodersha G. Polomski RE. Soundararajan N. Wang SSY. Org. Process Res. Dev.  2001,  5:  636 
• 10b Hlubucek J. Ritchie E. Taylor WC. Tetrahedron Lett.  1969,  1369 
• 10c Hlubucek J. Ritchie E. Taylor WC. Aust. J. Chem.  1971,  24:  2347 
• 11a Yadav JS. Reddy BVS. Rao TP. Tetrahedron Lett.  2000,  41:  7943 
• 11b Cossy J. Rakotoarisoa H. Kahn P. Desmurs J.-R. Tetrahedron Lett.  1998,  39:  9671 
• 12a North JT. Kronenthal DR. Pullockaran AJ. Real SD. Chen HY. J. Org. Chem.  1995,  60:  3397 
• 12b Tiabi M. Zamarlik H. Tetrahedron Lett.  1991,  32:  7251 
• 13a Portscheller JL. Malinakova HC. Org. Lett.  2002,  4:  3679 
• 13b Garcías X. Ballester P. Saá JM. Tetrahedron Lett.  1991,  32:  7739 
• 13c Goujon JY. Zammattio F. Kirschleger B. Tetrahedron: Asymmetry  2000,  11:  2409 
• 13d Tisdale EJ. Vong BG. Li H. Kim SH. Chowdhury C. Theodorakis EA. Tetrahedron  2003,  59:  6873 
• 14 Lee YR. Choi JH. Yoon SH. Tetrahedron Lett.  2005,  46:  7539 
• 15a Lee YR. Choi JH. Trinh DTL. Kim NW. Synthesis  2005,  3026 
• 15b Lee YR. Lee WK. Noh SK. Lyoo WS. Synthesis  2006,  853 
• 16 Kamperdick C. Van N H. Sung TV. Adam G. Phytochemistry  1997,  45:  1049 
• 17 Sabulal B. George V. Shiburaj S. J. Essent. Oil Res.  2006,  18:  462 
• 18a Li G.-L. Zeng J.-F. Song C.-Q. Zhu D.-Y. Phytochemistry  1997,  44:  1175 
• 18b Dictionary of Chinese Herbal Medicines   Vol. 1:  Jiangsu New Medical College, Shanghai Science and Technology Publishing House; Shanghai: 1986.  p.68 

19

This plant, a traditional Chinese herb, has antipyretic, anti-inflammatory, and analgesic activities and is used in traditional medicines for the treatment of trauma, abscesses, wound infections, eczema, and dermatitis.