Steroselective Intramolecular Cyclization Using Palladium Catalyst and Its Application to the Synthesis of Natsural Products

• Project/Area Number: 10640514
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Organic chemistry
• Research Institution: Toyama University
• Principal Investigator: HIRAI Yoshiro Faculty of Science, Toyama University Professor, 理学部, 教授 (70111747)
• Project Period (FY): 1998 – 1999
• Project Status: Completed (Fiscal Year 1999)
• Budget Amount: ¥3,300,000 (Direct Cost: ¥3,300,000); Fiscal Year 1999: ¥1,300,000 (Direct Cost: ¥1,300,000); Fiscal Year 1998: ¥2,000,000 (Direct Cost: ¥2,000,000)
• Keywords: stereoselective cyclization / palladium (II) catalyst / silver trifluoroacetate / trans(2,6)piperidine / trans(2,4)piperidine / (+)-prosopinine / (-)-SS20846A / (+)-Deoxymannojirimycin / パラジウム錯体 / 消化管運動抑制作用 / (S)-glycidol / 1-deoxymannojirimycin / グリコシダーゼ阻害作用 / アザ糖類

Research Abstract

The intramolecular cyclization of the optically active urethanes containing allylic alkohol was effected by treatment with bis(acetonitrile)palladium (II) chloride to give the trans(2,6)piperidine system as a single diastereoisomer. During these transformations, the Pd (II) species are not reduced and thus the catalyst can recycle without its reoxidation. On the other hand, cyclization of the simillar substrate containing allylic chloride using silver trifluoroacetate in the presence of sodium hydride afforded the cis(2,6)piperidine system. Cyclization of other substrates using these transition metal complexes was also examined and simillar results were obtained.
The cyclo-adducts obtained were proved to be useful chiral building blocks by their conversion into (+)-prosopinine, (-)-SS20846A, (+)-Deoxymannojirimycin, and (-)-hydroxysedamine, respectively

Research Products

• [Publications] 平井美朗: "2価のパラジウム触媒を用いる含窒素ヘテロ理の離伝い選択的な構築と天然物不斉合成への応用"有機合成化学協会誌. 56. 34-44 (1988)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] Hajime Yokoyama: "Total Synthesis of SS20846A via Intramolecular Pd(II)-catalyzed Cyclization"Tetrahedron Letters. 39. 5971-5974 (1998)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] Hajime Yokoyama: "Asymmetric Synthesis of Chiral 2-Fluorinated 1,3-propanediols and Its Application to the Preparation of Monofluorinated Chiral Synthon"Tetrahedron Letters. 39. 7741-7744 (1998)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] Hajime Yokoyama: "Palladium (II)-Catalyzed Cyclization of Urethanes and Total Synthesis of l-Deoxymannojrimycin"Organic Letters.
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] Hajime Yokoyama, Kumiko Otaya, Seiji Yamaguchi, and Yoshiro Hirai: "Total Synthesis of SS20846A via Intramolecular Pd(II)-catalyzed Cyclization"Tetrahedron Letters. 39. 5971-5974 (1998)
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] Hajime Yokoyama, Ryo Hydo, Akiko Nakada, Seiji, Yamaguchi, and Yoshiro Hirai, Tadashi Kometani, Michimasa Goto, Norio Shibata, and Yoshio Takeuchi: "Asymmetric Synthesis of Chiral 2-Fluorinated 1,3-Propanediols and Its Application to the Preparation of Monofluorinated Chiral Synthon"Tetrahedron Letters. 39. 7741-7744
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] Hajime Yokoyama, Kumiko Otaya, Machiko Sakou, Masahiro Miyazawa, Seiji Yamaguchi, and Yoshiro Hirai: "Palladium(II)-Catalyzed Cyclization of Urethanes and Total Synthesis of 1-Deoxymannojirimycin."Organic Letters. (submitted.).
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] 平井美朗: "2価のパラジウム触媒を用いる窒素ヘテロ環の立体選択的な構造と天然物不斉合成への応用"有機合成化学協会誌. 56. 34-44 (1988)
• [Publications] Hajime Yokoyama: "Total Synthesis of SS20846A via Intramolecular Pd(II)-catalyzed Cyclization"Tetrahedron Letters. 39. 5971-5974 (1998)
• [Publications] Hajime Yokoyama: "Asymmetric Synthesis of Chiral 2-Fluorinated 1,3-propan propanciol and Its Application to the Preparation of Monofluorinated Chiral synfhon"Tetrahedron Letters. 39. 7741-7744 (1998)
• [Publications] Hajime Yokoyama: "Palladium(II)-catalyzed Cyclization of Urethanes and Total Synthesis of 1-deoxymannojirimycin"Organic Letters.
• [Publications] Yoshiro Hirai 他3名: "Total Synthesis of SS20846A uia Intromolecutar Pc(CII)-catalyzed cyclization" TETRAHEDRON LETTERS. 39・33. 5971-5974 (1998)