Total Synthesis and Absolute Structure Determination of Marine Polyether Macrohdes.

• Project/Area Number: 14580606
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Bioorganic chemistry
• Research Institution: Hokkaido University
• Principal Investigator: FUJIWARA Kenshu Hokkaido Univ., Grad.School of Sci., Asso.Prof., 大学院・理学研究科, 助教授 (20222268)
• Project Period (FY): 2002 – 2003
• Project Status: Completed (Fiscal Year 2003)
• Budget Amount: ¥3,600,000 (Direct Cost: ¥3,600,000); Fiscal Year 2003: ¥1,200,000 (Direct Cost: ¥1,200,000); Fiscal Year 2002: ¥2,400,000 (Direct Cost: ¥2,400,000)
• Keywords: Marine Natural Products / Polyether Macrolide / Total Synthesis / Stereo-structure Determination / Pectenotoxins / Shellfish Poisoning / Cytotoxicity against Cancer Cells / Polyether Framework

Research Abstract

New methodologies for total synthesis and stereochemical assignment of marine polyether macrolides were investigated. In this project, pectenotoxin 2,a diarrhetic shellfish toxin isolated from scallop Patinopecten yessoensis and dinoflagellate Dinophysis fortii, and goniodomin A, an antifungal agent isolated from dinoflagellate Alexandrium hiranoi (Goniodoma pseudogoniaulax), were selected as the synthetic targets. Pectenotoxin 2 was planned to be derived from its 1-epi congener at the final stage of its total synthesis. Full-protected form of the 7-epi-pectenotoxin 2 was successfully synthesized from four segments corresponding to the C1-C7,C8-C20,C21-C30 and C31-C40 parts, through a convergent process including sulfone-coupling, acetal-cyclization, and-ring-closing-olefin-metathesis reactions. Partial synthesis of goniodomin A was planned for the stereochemical assignment. Synthesis of the C1-C7,C6-C16,C15-C25, and C31-C36 fragments were established.

Research Products

• [Publications] Kenshu Fujiwara: "Total Synthesis of Prelaureatin."Synlett. No.9. 1493-1495 (2002)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] Kenshu Fujiwara: "Synthesis of the D-,E-,F-, and I-Ring Part of Ciguatoxin by a Common Strategy Starting from Tri-O-acetyl-D-glucal"Synlett. No.9. 1496-1499 (2002)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] Kenshu Fujiwara: "Convergent Synthesis of the BDCE-Ring Part of Ciguatoxin"Synlett. No.11. 1835-1838 (2002)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] Hideki Tanaka: "Synthesis of the AB-Ring Segment for the Convergent Construction of the Left Half in Ciguatoxin"Tetrahedron. Vol.58,No.50. 10017-10031 (2002)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] K.Fujiwara, S.-i.Souma, H.Mishima, A.Murai: "Total Synthesis of Prelaureatin."Synlett. 2002(9). 1493-1495 (2002)
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] K.Fujiwara, Y.Koyama, E.Doi, K.Shimawaki, Y.Ohtaniuchi, A.Takemura, S.-i.Souma, A.Murai: "Syntheses of the D-, E-, F-, and I-Ring Parts of Ciguatoxin by a Common Strategy Starting from Tri-O-acetyl-D-glucal."Synlett. 2002(9). 1496-1499 (2002)
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] K.Fujiwara, Y.Koyama, K.Kawai, H.Tanaka, A.Murai: "Convergent Synthesis of the BCDE-Ring Part of Ciguatoxin"Synlett. 2002(11). 1835-1838 (2002)
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] H.Tanaka, K.Kawai, K.Fujiwara, A.Murai: "Synthes i s_of_thje_AB-Ring Segment for the Convergent Construction of the Left Half in Ciguatoxin"Tetrahedron. 58(50). 10017-10031 (2002)
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] Kenshu Fujiwara: "Total Synthesis of Prelaureatin"Synlett. No.9. 1493-1495 (2002)
• [Publications] Kenshu Fujiwara: "Syntheses of the D-, E-, F-, and I-Ring Parts of Ciguatoxin by a Common Strategy Starting from Tri-O-acetyl-D-glucal"Synlett. No.9. 1496-1499 (2002)
• [Publications] Kenshu Fujiwara: "Convergent Synthesis of the BCDE-Ring Part of Ciguatoxin"Synlett. No.11. 1835-1838 (2002)
• [Publications] Hideki Tanaka: "Synthesis of the AB-Ring Segment for the Convergent Construction of the Left Half in Ciguatoxin"Tetrahedron. Vol.58, No.50. 10017-10031 (2002)