Highly stereoselective reduction using palladium catalysis and its application to nitrogen containing biologically active substances

钯催化高度立体选择性还原及其在含氮生物活性物质中的应用

• 批准号: 02650634
• 负责人: SHIMIZU Isao
• 金额: $ 0.9万
• 依托单位: Waseda University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1990
• 资助国家: 日本
• 起止时间: 1990 至 1991
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-02650634/
• 关键词: Palladium Catalyst; Indolizidine Alkaloid; Alkenyl Oxirane; (-)-Nupharamine; Reduction with Formic Acid; (pi-Allyl) palladium Complex; ギ酸還元; (-)ーヌファラミン; (-)ーセリユルニン; アルアニルオキシラン

We have developed useful a synthetic method for preparation of nitrogen containing organic compounds using a palladium-catalyzed reaction as a key reaction. Thus, reaction of optically active alkenyl oxiranes and formic acid in the presence of a catalytic amount of palladium-phosphine complexes gives the optically active homoallylic alcohols, whose hydroxy group is substituted with a nitrogen atom selectively to give optically active amines. The delta-amino ketons or delta-amino esters obtained are cyclized to optically active piperidine or indolizidine compounds. Chiral synthesis (-)-nupharamine and the dendrobatid alkaloids 205A, 209B, and 235B were carried out from these compounds.

我们开发了一种有用的合成方法，使用钯催化反应作为关键反应来制备含氮有机化合物。因此，光学活性烯基环氧乙烷和甲酸在催化量的钯-膦络合物存在下反应得到光学活性高烯丙醇，其羟基被氮原子选择性取代以得到光学活性胺。将获得的δ-氨基酮或δ-氨基酯环化为光学活性哌啶或吲哚里西啶化合物。由这些化合物进行手性合成(-)-奴法拉明和树状生物碱205A、209B和235B。

项目成果

Isao shimizu, Hiroyuki yamazaki: ""Chiral synthesis of (-)-Nupharamine"" Chem. Lett.777-778 (1990)

Isao Shimizu、Hiroyuki yamazaki：“(-)-Nupharamine 的手性合成”Chem。

Kazuo Nagasawa: "Stereoselectire Synthesis of 1α-Hydroxyritamin D_3 A-Ring Synthons by Palladium-Catalyzed Cyclization" Tetrahedron hett.32. 4937-4941 (1991)

Kazuo Nagasawa：“通过钯催化环化立体选择性合成 1α-Hydroxyritamine D_3 A-Ring Synthons”Tetrahedron hett.32 4937-4941 (1991)。

Isao SHIMIZU: "Facile Allylation of 4,4,4-Trifluoroacetate by Palladium Catalysts." SynLett. (1992)

Isao SHIMIZU：“通过钯催化剂轻松烯丙基化 4,4,4-三氟乙酸酯。”

Isao shimizu, Naoto Matsuda, Yasuo Noguchi, Yoshiro Zako, KazuoNagasawa: ""Synthesis of Vitamin D_3 D Ring Synthons by Reductive Cleavage of Norbornan-6-one-2-carboxylates"" Tetrahedron Lett.31. 4899-4902 (1990)

Isao shimizu、Naoto Matsuda、Yasuo Noguchi、Yoshiro Zako、KazuoNagasawa：“通过 Norbornan-6-one-2- 羧酸酯的还原裂解合成维生素 D_3 D 环合成物””四面体 Lett.31。

Masato Oshima, Isao Shimizu, Akio Yamamoto, Fumiyuki Ozawa: ""Synthesis and Properties of (pi-Allyl) palladium Formates as Intermediates in Palladium-Cataalyzed Reductive Cleavage of Allylic Acetates and Carbonates with Formic Acid"" Organometallics. 10.

Masato Oshima、Isao Shimizu、Akio Yamamoto、Fumiyuki Ozawa：“作为钯催化甲酸乙酸烯丙酯和碳酸酯还原裂解中间体的（π-烯丙基）钯甲酸盐的合成和性能”有机金属化合物。