Development of Transition-metal Catalyzed Amination Process of Olefins Aimed for the Production of Physiologically Important Compounds

开发过渡金属催化烯烃胺化工艺，用于生产重要的生理化合物

• 批准号: 05555246
• 负责人: TAMARU Yoshinao
• 金额: $ 9.66万
• 依托单位: Nagasaki University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Developmental Scientific Research (B)
• 财政年份: 1993
• 资助国家: 日本
• 起止时间: 1993 至 1995
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-05555246/
• 关键词: Aminocarbonylation; Palladium Catalysis; Carbon monoxide; Chemoselectivity; Carbamate (endo-, exo-); Urea; ジエニルアミノ化; 一酸化炭素; アリルアミン

exo-Ureas, endo-ureas, exo-sulfonamides, and exo-carbamates readily undergo aminocarbonylation by the catalysis of PdC12 in methanol under 1 atm of carbon monoxide at room temperature. O-Allyl-endo-carbamates, on the other hand, do not undergo the aminocarbonylation under the similar conditions. This makes sharp contrast to the fact that endo-ureas are more reactive toward aminocarbonylation than exo-ureas. After experimentations, we found that aminocarbonylation of endo-carbamates proceed smoothly in the presence of sodium acetate and methyl orthoacetate (MOA). MOA can be utilized as an additive (in MeOH as a solvent) or as a solvent. In the latter case, MOA serves not only as a solvent but also as a reactant (a nucleophile) and much higher stereoselectivities are observed then the case undertaken in MOA/MeOH.Diamines possessing endo-carbamate and exo-carbamate (exo-urea or exo-sulfonamide) moieties in the same molecules were found to undergo chemoselective amination : the endo-carbamate moieties in MOA and the exo-carbamate, exo-urea, and exo-sulfonamide moieties in MeOH undergo the selective aminocarbonylation under 1 atm of CO by the catalysis of PbC12.

外-脲、内-脲、外-磺酰胺和外-氨基甲酸酯在室温下在1大气压一氧化碳下通过PdCl 2在甲醇中的催化容易地进行氨基羰基化。另一方面，O-烯丙基-内氨基甲酸酯在类似条件下不进行氨基羰基化。这与内脲比外脲对氨基羰基化更具反应性的事实形成鲜明对比。实验发现，在乙酸钠和原乙酸甲酯（MOA）存在下，氨基羰基化反应进行得很顺利。MOA可用作添加剂（在作为溶剂的MeOH中）或用作溶剂。在后一种情况下，MOA不仅用作溶剂，而且用作反应物与MOA/MeOH相比，MOA/MeOH具有更高的立体选择性。具有内氨基甲酸酯和外氨基甲酸酯的二胺发现相同分子中的（外-脲或外-磺酰胺）部分经历化学选择性胺化：MOA中的内-氨基甲酸酯部分和MeOH中的外-氨基甲酸酯、外-脲和外-磺酰胺部分在1个大气压的CO下通过PbCl 2催化进行选择性氨基羰基化。

项目成果

y.Tamaru, A.Tanaka, K.Yasui, S.Goto, S.Tanaka: "Highly Stereoselective Allylation of Aldehyde: Generation of Stereochemically Sefined Allylzinc Species via Alkyl-Allyl Exchange..." Angew. Chem. Int. Ed. Engl.34. 787-789 (1995)

y.Tamaru、A.Tanaka、K.Yasui、S.Goto、S.Tanaka：“醛的高度立体选择性烯丙基化：通过烷基烯丙基交换生成立体化学固定的烯丙基锌物种……”Angew。

K.Yasui: "Stereoselective Synthesis of Cyclopropanone Ketals via Silyl Chloride Promoted Cyclization of β-Zinciopropionates" Tetrahedron. 51. 6881-6900 (1995)

K. Yasui：“通过氯硅烷促进 β-丙酸锌的环化立体选择性合成环丙酮缩酮”，Tetrahedron，51。6881-6900 (1995)。

T.Bando: "Regio-and Stereoselective Synthesis of 1,3-Hydroxy Amines via Palladium-catalyzed Carbonate-Carbamate Trnsformation with Unique Stereoselectivity" J.Org.Chem.59. 1465-1474 (1994)

T.Bando：“通过具有独特立体选择性的钯催化碳酸酯-氨基甲酸酯转化来区域和立体选择性合成 1,3-羟基胺”J.Org.Chem.59。

Y.Tamaru: "Pronouced Electonic Effects of Allylic Amino Group on the pi‐Facial Stereoseletivity and Reactivity in Electrophilic Addition Reaction to Double Bonds" J.Chem.Soc.,Chem.Commun.,. 21. 1601-1602 (1993)

Y.Tamaru：“烯丙基氨基对双键亲电加成反应中 pi-Facial 立体选择性和反应性的显着电子效应”J.Chem.Soc.,Chem.Commun., 21. 1601-1602 (1993)

K.Yasui, S.Tanaka, and Y.Tamaru: "Stereoselective Synthesis of Cyclopropanone Ketals via Silyl Chloride Promoted Cyclization of β-Zinciopropionates"." Tetrahedrem. 51. 6881-6900 (1995)

K. Yasui、S. Tanaka 和 Y. Tamaru：“通过氯硅烷促进 β-四面体锌的环化立体选择性合成环丙酮缩酮”。 51. 6881-6900 (1995)。