Catalytic Asymmetric Total Synthesis of Several Biologically Active Natural Products

几种生物活性天然产物的催化不对称全合成

• 批准号: 10470462
• 负责人: SHIBASAKI Masakatsu
• 金额: $ 6.78万
• 依托单位: The University of Tokyo
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B).
• 财政年份: 1998
• 资助国家: 日本
• 起止时间: 1998 至 2000
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-10470462/
• 关键词: biologically active compound; strychinine; phorbol; wortmannin; catalytic enantioselective total synthesis; Michael reaction; catalytic kinetic resolution; intramolecular Heck reaction; 多機能不斉触媒; エポシロン; ジヒドロアクアマイシン; 触媒的不斉シアノシリル化反応; 直接的触媒的不斉アルドー

The project involves a development of new catalytic enantioselective reactions, and their application to a catalytic asymmetric synthesis of biologically active natural products, such as strychnine, wortmannin and phorbol ester. Using the catalytic enantioselective Michael reaction by heterobimetallic complexes, such as ALB or La-linked BINOL, a practical synthetic route for the intermediate of strychynine was established. Using a kinetic resolution by an enantioselective intramolecular Heck reaction, a synthetic intermediate of wortmannin was developed. Further investigations toward the total synthesis of these biologically important compounds are currently ongoing.

该项目涉及开发新的催化对映选择性反应，并将其应用于生物活性天然产物的催化不对称合成，如士的宁、Wortmannin和佛波酯。利用异双金属络合物(ALB或La-BINOL)催化的对映选择性Michael反应，建立了一条合成马钱子碱中间体的实用路线。通过对映体选择性分子内Heck反应的动力学拆分，合成了Wortmannin的合成中间体。对这些生物重要化合物的全合成的进一步研究目前正在进行中。

项目成果

K.Yamada,S.J.Harwood、H.groger,and M.Shibasaki: "The First Catalytic Asymmetric Nitro-Mannich-type Reaction Promoted by a New Heterobimetallic Complex"Angew.Chem.Int.Ed.. 38. 3504-3506 (1999)

K. Yamada、S. J. Harwood、H. groger 和 M. Shibasaki：“新型异双金属配合物促进的第一个催化不对称硝基曼尼希型反应”Angew Chem. 38. 3504-3506 ）

M.Sodeoka, M.A.Arai, K.Adachi, K.Uotsu and M.Shibasaki: "Rational Design, Synthesis, and Evaluation of a New Type of PKC Inhibitor" J.Am.Chem.Soc.120. 457-458 (1998)

M.Sodeoka、M.A.Arai、K.Adachi、K.Uotsu 和 M.Shibasaki：“新型 PKC 抑制剂的合理设计、合成和评估”J.Am.Chem.Soc.120。

F.Miyazaki, K.Uotsu and M.Shibasaki: "Silver Salt Effects on an Asymmetric Heck Reaction. Catalytic Asymmetric Total Synthesis of(+)- Xestoquinone." Tetrahedron. 54. 13073-13078 (1998)

F.Miyazaki、K.Uotsu 和 M.Shibasaki：“银盐对不对称 Heck 反应的影响。( )- Xestoquinone 的催化不对称全合成。”

S.Shimizu, K.Ohori, T.Arai, H.Sasai and M.Shibasaki: "A Catalytic Asymmetric Synthesis of Tubifolidine" J.Org.Chem.63. 7547-7551 (1998)

S.Shimizu、K.Ohori、T.Arai、H.Sasai 和 M.Shibasaki：“Tubifolidine 的催化不对称合成”J.Org.Chem.63。

K.Yamakoshi,S.Harwood,M.Kanai and M.Shibasaki: "Catalytic Asymmetic Addition of Diphenyphosphine Oxide to Cyclic Imines"Tetrahedron Lett. 40. 2565-2568 (1999)

K.Yamakoshi、S.Harwood、M.Kanai 和 M.Shibasaki：“二苯膦氧化物与环状亚胺的催化不对称加成”四面体莱特。