Studies on catalysts for selective functionalization of Group 14 compounds

14族化合物选择性官能化催化剂的研究

• 批准号: 09650953
• 负责人: TSUJI Yasushi
• 金额: $ 1.92万
• 依托单位: HOKKAIDO UNIVERSITY (1998)Gifu University (1997)
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1997
• 资助国家: 日本
• 起止时间: 1997 至 1998
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09650953/
• 关键词: functionalization; cyanation; palladium catalyst; catalyst species; oxidative addition; fluxional; 触媒素反応; 酸化的付加反応; ビス(シリル)錯体; ビス(スタニル)錯体; 単分子分子内回転; X線構造; 錯体触媒; 反応機構; 白金錯体; パラジウム錯体

Allylic carbonates are cyanated in high yields to beta, gamma-unsaturated carbonitriles using trimethylsilyl cyanide in the presence of catalytic amount (5 mol%) of Pd(PPh_3)_4 in THF under reflux. The cyanations of several cis- and trans-alicyclic substrates proceed cleanly (stereoselectivity> 99%) with overall retention. Characterization and reaction of palladium complexes relevant to the present catalysis indicate that transmetallation of eta^3-allyl palladium complex with trimethylsilyl cyanide is facile, while the resulting cyano(eta^3-allyl)palladium complexes afford the corresponding allylic cyanides only when excess trimethylsilyl cyanide is present. Stereochemistry of the product indicates that the CN attacks the eta^3-allyl moieties from the palladium side.The structures and fluxional behavior of two cis-bis(silyl)bis(phosphine)platinum complex, cis- [Pt(SiPh_2Me)_2(PMe_2Ph)_2] and cis-[Pt(SiFMe_2)_2(PEt_3)_2], and two cis-bis(stannyl)bis(phosphine)palladium complex, cis-[Pd(SnMe_3)_2(PMe_3)_2] and cis-[Pd(SnMe_3)_2(PMePh_2)_2], were examined, The complexes have twisted square-planar structures with cis-orientation of the ligands. The bis(silyl)platinum complexes show fluxional behavior on the NMR time-scale. In the fluxional process, the spin-spin coupling between P, Si, and Pt are retained ; namely these nuclear spin states are intramolecularly conserved. The fluxionality of the complexes is attributed to the unimolecular twist-rotation via pseudo tetrahedral transition state. Similar fluxionality of the bis(stannyl)palladium complex is evident by utilizing both solution and solid state ^<31>P NMR.

在催化量（5mol%）Pd（PPh_3）_4存在下，用三甲基硅腈将烯丙基碳酸酯氰化成β，γ-不饱和腈。几种顺式和反式脂环底物的氰化反应干净地进行（立体选择性> 99%），具有总体保留。与本催化剂相关的钯络合物的表征和反应表明，eta^3-烯丙基钯络合物与三甲基硅基氰化物的转移是容易的，而所得氰基（eta^3-烯丙基）钯络合物仅在过量的三甲基硅基氰化物存在时才提供相应的烯丙基氰化物。产物的立体化学研究表明，CN从钯侧进攻烯丙基。（膦）铂络合物，顺- [Pt（SiPh_2Me）_2（PMe_2Ph）_2]和cis-[Pt（SiFMe_2）_2（PEt_3）_2]以及两个cis-双（甲锡烷基）双研究了顺式-[Pd（SnMe_3）_2（PMe_3）_2]和顺式-[Pd（SnMe_3）_2（PMePh_2）_2]两种膦钯配合物的结构。双硅基铂配合物在核磁共振时间尺度上表现出流动性。在流动过程中，P，Si和Pt之间的自旋-自旋耦合被保留;即这些核自旋态是分子内守恒的。配合物的流动性是通过假四面体过渡态的单分子扭曲-旋转作用而产生的。双（甲锡烷基）钯络合物的类似流动性通过利用溶液和固态11 P NMR两者是明显<31>的。

项目成果

Y.Tsuji et al.: "Structure and Facile Unimolecular Twist-Rotation of cis-Bis (silyl) bis (phosphine) platinum and cis-Bis (stannyl) bis (phosphine) palladium Complexes" Organometallics. 17. 507-512 (1998)

Y.Tsuji 等人：“顺式双（甲硅烷基）双（膦）铂和顺式双（锡基）双（膦）钯配合物的结构和简易单分子扭转旋转”有机金属学。

Y.Tsuji: "Structure and Facile Unimolecular Twist-Rotation of cis-Bis(silyl)bis(phosphine)-platinum and cis-Bis(stannyl)bis(phosphine)palladium Complexes" Organometallics. 17. 507-512 (1998)

Y.Tsuji：“顺式双（甲硅烷基）双（膦）-铂和顺式-双（锡基）双（膦）钯配合物的结构和简易单分子扭转旋转”有机金属学。

Y.Tsuji, K.Nishiyama, S-I.Hori, M.Ebihara, T.Kawamura: "Structure and Facile Urimolecular Twist-Rotation of cis-Bis(silyl)bis(phosphine)-platinum and cis-Bis(stannyl)bis(phosphine)palladium Conplexes" Organometallics. 17(印刷中). (1998)

Y.Tsuji、K.Nishiyama、S-I.Hori、M.Ebihara、T.Kawamura：“顺式双（甲硅烷基）双（膦）-铂和顺式双（锡基）双（的结构和简单的尿分子扭转旋转） (1998)

Y.Tsuji et al.: "Palladium-Complex-Catalyzed cyanation of Allylic Carbonates and Acetates Using Trimethylsilyl Cyanide" Organometallics. 17. 4835-4841 (1998)

Y.Tsuji 等人：“使用三甲基甲硅烷基氰化物的钯配合物催化烯丙碳酸酯和乙酸酯的氰化”有机金属。

Y.Tsuji: "Palladium-Complex-Catalyzed Cyannation of Allylic Carbonates and Acetates Using Trimethylsilyl Cyanide" Organometallics. 17. 4835-4841 (1998)

Y.Tsuji：“使用三甲基甲硅烷基氰化物的钯络合物催化烯丙碳酸酯和乙酸酯的氰化”有机金属。