(C5Me5)Y(CH2C6H4NMe2-o)2 | 1271455-34-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (C5Me5)Y(CH2C6H4NMe2-o)2
• 英文别名: [(η5-pentamethylcyclopentadienyl)Y(N,N,2-trimethylaniline(-H))2]；2-methanidyl-N,N-dimethylaniline;1,2,3,4,5-pentamethylcyclopenta-1,3-diene;yttrium(3+)
• CAS: 1271455-34-5
• 化学式: C₂₈H₃₉N₂Y
• 分子量: 492.537
• InChiKey: CSVQQXITEDFGBH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.81
• 重原子数：
  31
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  6.5
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (C5Me5)Y(CH2C6H4NMe2-o)2 、 氘 以 四氢呋喃 为溶剂， 以47%的产率得到[((η5-pentamethylcyclopentadienyl)Y)5(μ5-D)(μ3-D)4(μ-D)5(tetrahydrofuran)2]
  参考文献：
  名称：

  Tetra-, Penta-, and Hexanuclear Yttrium Hydride Clusters from Half-Sandwich Bis(aminobenzyl) Complexes Containing Various Cyclopentadienyl Ligands

  摘要：

  The novel series of half-sandwich tetrahydrofuran (THF)-free yttrium bis(arninobenzyl) complexes [(C(5)Me(4)R)-Y(CH(2)C(6)H(4)NMe(2-o))(2)] (R = SiMe(3) (1a), Me (1b), Et (1c), H (1d)) was prepared by treatment of [Y(CH(2)C(6)H(4)NMe(2-o))(3)] with C(5)Me(4)RH, and their reactions with H(2) and with PhSiH(3) in aromatic solvents or in THF were examined. The reaction of la with H(2) in benzene gave the pentanudear yttrium decahydride complex [{Cp'Y(mu-H)(2)}(5)] (Cp' = eta(5)-C(5)Me(4)SiMe(3)) (3), which could not be obtained by the reaction of the corresponding THF-coordinated dialkyl complex [Cp'Y(CH(2)SiMe(3))(2)(THF)] with H(2). The reaction of 1b with H(2) in toluene gave the partially hydrogenated tetranudear mixed aminobenzyl/hydride complex [(Cp*Y)(2)(CH(2)C(6)H(4)NMe(2-o))(mu-H)(3)](2) (4; Cp* = eta(5)-C(5)Me(5)), and no further hydrogenation reaction occurred, whereas the corresponding reaction of 1b with H(2) in THF gave the pentanuclear yttrium polyhydride complex [{Cp*Y(mu-H)(2)}(5) (THF)(2)] (5). Hydrogenolysis of the sterically less demanding C(5)Me(4)H-ligated complex 1d with H(2) in THF gave the tetranuclear octahydride complex [{Cp(H)Y(mu-H)(2)}(4)(THF)(4)] (6; Cp(H) = eta(5)-C(5)Me(4)H), which has one coordinating THF ligand on each metal atom. The hexanuclear yttrium dodecahydride complex {[Cp*Y(mu-H)(2)](6)} (7) was obtained by treatment of 1b with PhSiH(3) in benzene. The structures of 1a,b,d, 3, 4, {{(C(5)Me(4)Et)Y(mu-H)(2)}(5)(THF)(2)] (5'), 6, and 7 were determined by X-ray single-crystal diffraction studies.

  DOI：

  10.1021/om1012055
• 作为产物：
  描述：

  Y(CH₂C₆H₄NMe₂-o)₃ 、 1,2,3,4,5-五甲基环戊二烯 以 四氢呋喃 为溶剂， 以68%的产率得到(C5Me5)Y(CH2C6H4NMe2-o)2
  参考文献：
  名称：

  Tetra-, Penta-, and Hexanuclear Yttrium Hydride Clusters from Half-Sandwich Bis(aminobenzyl) Complexes Containing Various Cyclopentadienyl Ligands

  摘要：

  The novel series of half-sandwich tetrahydrofuran (THF)-free yttrium bis(arninobenzyl) complexes [(C(5)Me(4)R)-Y(CH(2)C(6)H(4)NMe(2-o))(2)] (R = SiMe(3) (1a), Me (1b), Et (1c), H (1d)) was prepared by treatment of [Y(CH(2)C(6)H(4)NMe(2-o))(3)] with C(5)Me(4)RH, and their reactions with H(2) and with PhSiH(3) in aromatic solvents or in THF were examined. The reaction of la with H(2) in benzene gave the pentanudear yttrium decahydride complex [{Cp'Y(mu-H)(2)}(5)] (Cp' = eta(5)-C(5)Me(4)SiMe(3)) (3), which could not be obtained by the reaction of the corresponding THF-coordinated dialkyl complex [Cp'Y(CH(2)SiMe(3))(2)(THF)] with H(2). The reaction of 1b with H(2) in toluene gave the partially hydrogenated tetranudear mixed aminobenzyl/hydride complex [(Cp*Y)(2)(CH(2)C(6)H(4)NMe(2-o))(mu-H)(3)](2) (4; Cp* = eta(5)-C(5)Me(5)), and no further hydrogenation reaction occurred, whereas the corresponding reaction of 1b with H(2) in THF gave the pentanuclear yttrium polyhydride complex [{Cp*Y(mu-H)(2)}(5) (THF)(2)] (5). Hydrogenolysis of the sterically less demanding C(5)Me(4)H-ligated complex 1d with H(2) in THF gave the tetranuclear octahydride complex [{Cp(H)Y(mu-H)(2)}(4)(THF)(4)] (6; Cp(H) = eta(5)-C(5)Me(4)H), which has one coordinating THF ligand on each metal atom. The hexanuclear yttrium dodecahydride complex {[Cp*Y(mu-H)(2)](6)} (7) was obtained by treatment of 1b with PhSiH(3) in benzene. The structures of 1a,b,d, 3, 4, {{(C(5)Me(4)Et)Y(mu-H)(2)}(5)(THF)(2)] (5'), 6, and 7 were determined by X-ray single-crystal diffraction studies.

  DOI：

  10.1021/om1012055
• 作为试剂：
  描述：

  2,6-二甲基吡啶 、 4-氯苯乙烯 在 [(phenyl)₃C][B(C₆F₅)₄] 、 (C5Me5)Y(CH2C6H4NMe2-o)2 作用下， 以 甲苯 为溶剂， 反应 24.0h， 以74%的产率得到2-[3-(4-Chlorophenyl)propyl]-6-methylpyridine
  参考文献：
  名称：

  钇催化的苯甲酰C的加成反应？烷基吡啶与烯烃的氢键

  摘要：

  阳离子半三明治式钇钇烷基络合物催化二烷基吡啶向各种烯烃（如乙烯，1-己烯，苯乙烯和1,3-共轭二烯）的邻位选择性苄基CH加成，以提供新的烷基化和烯丙基化的吡啶衍生物（参见方案； Cp ＝ C 5 Me 5）。阳离子半夹心钇吡啶甲基物种，如[CPY（2-CH 2 -6-CH 3 Ç 5 ħ 3 N）] +，已被证实是在这一转变的关键活性物质。

  DOI：

  10.1002/anie.201208867

文献信息

• Divergent Synthesis of Multi‐Substituted Aminotetralins via [4+2] Annulation of Aldimines with Alkenes by Rare‐Earth‐Catalyzed Benzylic C(sp³)−H Activation
  作者：Xuefeng Cong、Qingde Zhuo、Na Hao、Aniket Mishra、Masayoshi Nishiura、Zhaomin Hou

  DOI：10.1002/anie.202318203

  日期：2024.3.22

  The search for efficient and selective methods for the divergent synthesis of multi‐substituted aminotetralins is of much interest and importance. We report herein for the first time the diastereoselective [4+2] annulation of 2‐methyl aromatic aldimines with alkenes via benzylic C(sp³)−H activation by half‐sandwich rare‐earth catalysts, which constitutes an efficient route for the divergent synthesis of both trans and cis diastereoisomers of multi‐substituted 1‐aminotetralin derivatives from readily accessible aldimines and alkenes. The use of a scandium catalyst bearing a sterically demanding cyclopentadienyl ligand such as C₅Me₄SiMe₃ or C₅Me₅ exclusively afforded the trans‐selective annulation products in the reaction of aldimines with styrenes and aliphatic alkenes. In contrast, the analogous yttrium catalyst, whose metal ion size is larger than that of scandium, yielded the cis‐selective annulation products. This protocol features 100 % atom‐efficiency, excellent diastereoselectivity, broad substrate scope, and good functional group compatibility. The reaction mechanisms have been elucidated by kinetic isotope effect (KIE) experiments and the isolation and transformations of some key reaction intermediates.

  摘要寻找多取代氨基四氢萘分歧合成的高效和选择性方法非常重要。我们在此首次报道了半三明治稀土催化剂通过苄基 C(sp3)-H 活化 2-甲基芳香醛与烯烃的非对映选择性[4+2]环化反应，这为从容易获得的醛和烯烃中发散合成多取代 1-氨基四氢萘衍生物的反式和顺式非对映异构体提供了一条有效途径。在醛亚胺与苯乙烯和脂肪烯的反应中，使用带有立体要求高的环戊二烯配体（如 C5Me4SiMe3 或 C5Me5）的钪催化剂只能得到反式选择性环化产物。与此相反，金属离子尺寸大于钪的类似钇催化剂则产生顺式选择性环化产物。该方案具有 100% 的原子效率、出色的非对映选择性、广泛的底物范围和良好的官能团兼容性。通过动力学同位素效应（KIE）实验以及一些关键反应中间体的分离和转化，阐明了反应机理。