Studies on the chemical-regulation of marine sessile organisms using phloroglucinol compounds from Eucalyptus sp

• Project/Area Number: 10660108
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Bioproduction chemistry/Bioorganic chemistry
• Research Institution: Shizuoka University
• Principal Investigator: ETOH Hideo Shizuoka University, Faculty of Agriculture, Professor, 農学部, 教授 (10076747)
• Co-Investigator(Kenkyū-buntansha): TERADA Yukimasa Meijo University, Faculty of Pharmacy, Associate Professor, 薬学部, 助教授 (20076756)
• Project Period (FY): 1998 – 2000
• Project Status: Completed (Fiscal Year 2000)
• Budget Amount: ¥3,600,000 (Direct Cost: ¥3,600,000); Fiscal Year 2000: ¥500,000 (Direct Cost: ¥500,000); Fiscal Year 1999: ¥800,000 (Direct Cost: ¥800,000); Fiscal Year 1998: ¥2,300,000 (Direct Cost: ¥2,300,000)
• Keywords: Eucalyptus / phlorogulucinol / marine sessile organisms / sideroxyronal / attaching repellent / strcuture-activity relationship / biofouling substance

Research Abstract

In this research we had the following two results. 1) The synthesis of grandinal : We prepared grandinol by an alternate and improved procedurein three steps in 13% yield. Synthesis of the jensenone derivative was started 1,3,5-trimethoxybenzene. n isovaleryl group was readily introduced by a reaction with isovaleryl chloride. Reduction of the isovaleryl trimethoxybenzene with LAH and subsequent dehydration by irradiation in CHCl_3 gave the styrene compound. Further, the styrene compound was reduced by treatment with Pt2O under H2 atmosphere to yield the alkylbenzene. By aromatic bromination, adding ClCO_2Me, elimination, reduction and oxidation, the jensenone derivative was synthesized in nine steps in 13% overall yiels. Having successfull prepared the desired compounds, the jensenone derivative was subjected to Diels-Alder cycloaddition. The desired product in 14% yield and the regio isomer in 18% yield were given. Finally, the desired product was subjected to deprotection of the hydroxy groups with BBr_3S(Me)_2. We accomplished the first synthesis of grandinal. 2) Structure-activity relationship of phloroglucinol compounds. We discuss the structure-activity relationship of phloroglucinol compounds on the basis of molecular mechanics caluculations. When these compounds were superimposed on each other and the strongest inhibitor was applied as a template, the repulsion energy of the other compounds was proportional to the logarithmic attachment-inhibiting activity. It is concluded that, of the two phloroglucinol rings in sideroxylonal A, ring C is more important, and those compounds that stereo-chemically and electrostationally resemple the template molecule are more active.

Research Products

• [Publications] Takuya Matsumoto: "The first total synthesis of grandinal, new phloroglucinol derivative isolated from Eucalyptus grandis"Chemistry Letters. 3(in press). (2001)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] Matstumoto, T., Singh, I.P., Etoh, H., and Tanaka H.: "The first total synthesis of grandinal, new phloroglucinol derivative isolated from Eucalyptus grandis"Chemistry Letters. (in press). (2001)
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] Takuya Matsumoto: "The first total synthesis of grandinal, new phloroglucinol derivative isolated from Eucalyptus grandis"Chemistry Letters. 3(in press). (2001)
• [Publications] Yukimasa Terada: "Structure-activity relationship of phloroglucinol compounds from Eucalyptus as marine antifoulants" Bioscience,Biotechnology and Biochemistry. 63・2. 276-280 (1999)