Total Synthesis of Complex Natural Products

• Project/Area Number: 08245103
• Research Category: Grant-in-Aid for Scientific Research on Priority Areas
• Allocation Type: Single-year Grants
• Research Institution: The Kitasato Institute (1998); Tokyo Institute of Technology (1996-1997)
• Principal Investigator: KUWAJIMA Isao The Kitasato Institute, Research Director, 生物機能研究所, 部長 (50016086)
• Co-Investigator(Kenkyū-buntansha): KOBAYASHI Susumu Science University of Tokyo, Department of Pharmaceutical Sciences, Professor, 薬学部, 教授 (70101102) ; KITAHARA Takeshi University of Tokyo, Graduate School of Agricultural and Life Sciences, Professor, 大学院・農学生命科学研究科, 教授 (40087573) ; OHFUNE Yasufumi Osaka City University, Faculty of Sciences, Professor, 理学部, 教授 (20142078) ; MURAI Akio Hokkaido University, Graduate School of Science, Professor, 大学院・理学研究科, 教授 (20000838) ; SUZUKI Keisuke Tokyo Institute of Technology, Graduate School of Science and Engineering, Professor, 大学院・理工学研究科, 教授 (90162940) ; 平間 正博 東北大学, 大学院・理学研究科, 教授 (30165203) ; 高橋 孝志 東京工業大学, 工学部, 教授 (80110724) ; 磯部 稔 名古屋大学, 農学部, 教授 (00023466)
• Project Period (FY): 1996 – 1998
• Project Status: Completed (Fiscal Year 1998)
• Budget Amount: ¥131,800,000 (Direct Cost: ¥131,800,000); Fiscal Year 1998: ¥35,500,000 (Direct Cost: ¥35,500,000); Fiscal Year 1997: ¥39,600,000 (Direct Cost: ¥39,600,000); Fiscal Year 1996: ¥56,700,000 (Direct Cost: ¥56,700,000)
• Keywords: Complex Natural Products / Taxusin / Taxol / Radicicol / Pironectin / Furaquinocine / Polycavernoside / Enantioselective Total Synthesis / タキソール / ゾアンタミン / タキソ-ル / オーストラリフンジン / ネオカルジノスタチン / 不斉合成 / テトロドトキシン / テルペンシン

Research Abstract

Total syntheses of complex natural products have been studied in this research group. During this investigation, taxane diterpene was one of major synthetic targets, and enantioselective total syntheses of (+)-taxusin and (-)-taxol have been efficiently achieved based on the B ring cyclization methodology of AC fragment.
Other representative natural products synthesized during this research period are radicicol, pironectin, tanabalin, furaquinocine, and polycavernoside.
Synthtic studies on α,α-disubstituted α-amino acid sub-structure, zoanthamine/nor-zoanthamine alkaloids, and ravidomycin were also developed.

Research Products

• [Publications] 桑嶋功: "Enantioselective Total Synthesis of Taxol"J.Am. Chem.Soc.. 120・49. 12980-12981 (1998)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] 桑嶋功: "Enantioselective Total Synthesis of (+)-Taxusin"J.Am. Chem.Soc.. 121(印刷中). (1999)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] 北原武: "Total Synthesis of (-)-Pironectin"Tetrahedron Lett. 39・45. 8313-8316 (1998)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] 小林進: "Synthetic Studies on Zoanthamine/Norzoanthamine Alkaloids : Construction of the Heterocyclic Aminal Core (CDEFG Ring)"Tetrahedron Lett. 39・34. 6241-6244 (1998)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] 鈴木啓介: "Total Synthesis of the Furaquinocins"J.Am. Chem.Soc.. 120・45. 11633-11644 (1998)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] 村井章夫: "Total Synthesis and Absolute Configuration of Polycavernoside A"J.Am. Chem.Soc.. 120・41. 10770-10771 (1998)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] I. Kuwajima: "Enantioselective Total Synthesis of Taxol"J. Am. Chem. Soc.. 120, No.49. 12980-12981 (1998)
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] I. Kuwajima: "Enantioselective Total Synthesis of (+)-Taxusin"J. Am. Chem. Soc.. 121, No.13. 3072-3082 (1999)
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] T. Kitahara: "Total Synthesis of (-)-Pironectin"Tetrahedron Lett.. 39, No.45. 8313-8316 (1998)
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] S. Kobayashi: "Synthetic Studies on Zoanthamine/Norzoanthamine Alkaloids : Construction of the Heterocyclic Aminal Core (CDEFG Ring)"Tetrahedron Lett.. 39, No.34. 6241-6244 (1998)
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] K. Suzuki: "Total Synthesis of Furaquinocins"J. Am. Chem. Soc.. 120, No.45. 11633-11644 (1998)
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] A. Murai: "Total Synthesis and Absolute Configuration of Polycavernoside A"J. Am. Chem. Soc.. 120, No.41. 10770-10771 (1998)
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] 桑嶋 功: "Enantioselective Total Synthesis of Taxol" J.Am.Chem.Soc.120・49. 12980-12981 (1998)
• [Publications] 桑嶋 功: "Enantioselective Total Synthesis of (+)-Taxusin" J.Am.Chem.Soc.121 印刷中. (1999)
• [Publications] 北原,武: "Total Synthesis of(-)-Pironectin" Tetrahedron Lett,. 39・45. 8313-8316 (1998)
• [Publications] 小林 進: "Synthetic Studies on Zoanthamine/Norzoanthamine Alkaloids : Construction of the Heterocyclic Aminal Core(CDEFG Ring)" Tetrahedron Lett.39・34. 6241-6244 (1998)
• [Publications] 鈴木 啓介: "Total Synthesis of the Furaquinocins" J.Am.Chem.Soc.120・45. 11633-11644 (1998)
• [Publications] 村井 章夫: "Total Synthesis and Absolute Configuration of Polycavernoside A" J.Am.Chem.Soc.120・41. 10770-10771 (1998)
• [Publications] I.Kuwajima: "A New Approach for Ingenol Synthesis" J.Org.Chem.119・NO,13. 3032-3033 (1997)
• [Publications] T.Kitahara: "Total Synthesis of Phenazinomycin and its Enantimer via High Pressue Reactior" Tetrahedron Lett.38・NO,28. 4993-4997 (1997)
• [Publications] S.Kobayashi: "Synthesis of 2-O-(3-O-Carbamoyl-a-D-mannopyranosyl)-L-glucopyranose : Suger Moiety of Antitumor Antibiotic Bleomycin" Tetrahedron. 53. 10993-11006 (1997)
• [Publications] K.Suzuki: "C-Glycosyl Juglone in Angucycline Synthesis : Total Synthesis of Galtamycinone Common Aglycon of C-Glycosyl Naphthacenequinone-Type Angucyclines" Tetrahedron. 53. 16533-16544 (1997)
• [Publications] T.Takahashi: "Synthesis of Taxoid Ring Systems:AC→ABC Approach by Way of Intramolecular Alkylation" Angew.Chem.,Int.Ed.Engl.36. 1319-1321 (1997)
• [Publications] M.Hirama: "Synthetic Study of Kedarcidin Chromophore:Advanced Models and Their Chemical Behavior" Synlett. NO,3. 250-252 (1997)
• [Publications] I.Kuwajima: "Total Synthesis of(±)-Taxusin" J.Am.Chem.Soc.118・NO.38. 9186-9187 (1996)
• [Publications] M.Isobe: "Pseudoenantiomeric Heteroconjugate Addition Approach for Synthesis of Segment C of Tautomycin" Tetrahedron,. 52・NO.8. 2877-2892 (1996)
• [Publications] S.Kobayashi: "Stereoselective Route of the Highly Oxidized Sidechain Moiety of Terpentecin and Related Antibiotics." Chem.Lett.NO.11. 931-932 (1996)
• [Publications] K.Suzuki: "On the Stereochemistry of Ary C-Glycosides:Unusual Behavior of Bis TBDPS Protected Aryl C-Olivosides" Tetrahedron Lett.37・NO.5. 663-666 (1996)
• [Publications] T.Takahashi: "Synthesis of Taxoid Ring System:AC→ABC Approach by Way of Intramolecular Alkylation" Angew.Chem.in press
• [Publications] M.Hirama: "Efficient Synthesis of a Carbocyclic Core Moiety with the Stereochemisty of the C-1027 Chromophore" Tetrahedron Lett.37・NO.29. 5135-5138 (1996)