1-[2,2-bis(3,5-dimethylpyrazol-1-yl)-1-tert-butylethyl]-1,3-cyclopentadiene | 1013932-07-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: 1-[2,2-bis(3,5-dimethylpyrazol-1-yl)-1-tert-butylethyl]-1,3-cyclopentadiene
• 英文别名: 1-[(2R)-2-cyclopenta-1,3-dien-1-yl-1-(3,5-dimethylpyrazol-1-yl)-3,3-dimethylbutyl]-3,5-dimethylpyrazole
• CAS: 1013932-07-4
• 化学式: C₂₁H₃₀N₄
• 分子量: 338.496
• InChiKey: VWLQURVZAPUMLV-LJQANCHMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5
• 重原子数：
  25
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.52
• 拓扑面积：
  35.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1-[2,2-bis(3,5-dimethylpyrazol-1-yl)-1-tert-butylethyl]-1,3-cyclopentadiene 、 (三甲基硅基)甲基氯化镁 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 、 乙醚 为溶剂， 反应 1.5h， 以88%的产率得到[Mg(CH₂SiMe₃)(κ²-η⁵-bpztcp)]
  参考文献：
  名称：

  New Racemic and Single Enantiopure Hybrid Scorpionate/Cyclopentadienyl Magnesium and Zinc Initiators for the Stereoselective ROP of Lactides

  摘要：

  The preparation of the first racemic bis(pyrazol-1-yl)rnethane-based NNCp-donor hybrid scorpionate/cyclopentadienyl magnesium and zinc complexes [Mg(R)(kappa(2)-eta(5)-NNCp)] (1-6) [NNCp = bpztcp, R = Me (1), Et (2), CH2SiMe3 (3); bpzpcp, R = Me (4), Et (5), CH2SiMe3 (6)] and [Zn(R)(kappa(2)-eta(1)-NNCp)] (7-12) [NNCp = bpztcp, R = Me (7), Et (8), CH2SiMe3 (9); bpzpcp, R = Me (10), Et (11), CH2SiMe3 (12)] has been carried out by the reaction of the corresponding racemic NNCp-H-donor scorpionate pro-ligands with Grignard reagents RMgCl, after deprotonation with (BuLi)-Bu-n, or directly with ZnR2. The resulting alkyl magnesium complexes (1-6) have been employed in a protonolysis reaction with 2,6-dimethylphenol to yield the aryloxide magnesium complexes [Mg(OAr)(kappa(2)-eta(5)-NNCp)] (13 and 14) [NNCp = bpztcp (13), bpzpcp (14)]. Subsequently, the enantiopure scorpionate pro-ligand (R,R)-bpmycpH (16a) {bpmycpH = 1-{2,2-bis (3,5-dimethyl-1H-pyrazol-1-yl)-1-(2R)-2-[(1R)-6,6-[3.1.1]-2-hepten-2-yl]]ethyl}-cyclopentadiene} and (R,R)-bpmycpH (16b) {bpmycpH = 2-{2,2-bis(3,5-dimethyl-1H-pyrazol-1-yl)-1-(2R)-2-[(1R)-6,6-[3.1.1]-2-hepten-2-yl]ethyl}cyclopentadiene} reacted with RMgCl (after addition of nBuLi) or with ZnR2 to give the single enantiopure complexes [Mg(R)(kappa(2)-eta(2)-R,S-bpmycp)] (17-19) (R = Me (17), Et (18), CH2SiMe3 (19)) {R,S-bpmycp = 2-{2,2-bis (3,5-dimethyl-1H-pyrazol-1-yl)-1-(2S)-2-[(1R)-6,6-[3.1.1]-2-hepten-2-yl]ethyl}cyclopentadienyl} and [Zn (R) (kappa(2)-eta(1)-R,S-bpmycp)] (20-22) (R = Me (20), Et (21), CH2SiMe3 (22)). The structures of these complexes were elucidated by H-1 and C-13{H-1} NMR spectroscopy, and the X-ray crystal structures of 2, 3, 7 and 21 were also established. These racemic and single enantiopure complexes 1-3, 5-9, 11-14, 19, and 21 can act as single-component initiators for the ring-opening polymerization of rac-lactide under mild conditions. Microstructural analysis of poly(rac-lactide)s revealed that, whereas the myrtenal substituent on the single enantiomerically pure initiator 21 exerts an appreciable influence on the degree of stereoselectivity to produce isotactic-enriched poly(lactide)s with a P-i value up to 0.77, the racemic mixtures of initiators impart more discrete levels of heteroselectivity in the production of PLAs, with a P-s, value of 0.72.

  DOI：

  10.1021/acs.organomet.5b00248

文献信息

• Scandium and Yttrium Complexes Supported by NNCp Heteroscorpionate Ligands: Synthesis, Structure, and Polymerization of ϵ-Caprolactone
  作者：Antonio Otero、Juan Fernández-Baeza、Antonio Antiñolo、Agustín Lara-Sánchez、Emilia Martínez-Caballero、Juan Tejeda、Luis F. Sánchez-Barba、Carlos Alonso-Moreno、Isabel López-Solera

  DOI：10.1021/om701033r

  日期：2008.3.1

  scorpionate/cyclopentadiene compounds with [M(CH2SiMe3)3(THF)3] (M = Sc, Y) afford the dialkyl complexes [M(CH2SiMe3)2(bpzcp)] (M = Sc (3), Y (4)) and [M(CH2SiMe3)2(bpztcp)] (M = Sc (5), Y (6)). The cationic alkyl complexes [M(CH2SiMe3)(bpzcp)]+ (M = Sc (7), Y (8)) were also prepared by the reaction of complexes 3 and 4 with [CPh3][B(C6F5)4] in THF. The structures of these compounds were determined by spectroscopic

  两种蝎子/环戊二烯区域异构体-bpzcpH（1- [2,2-双（3,5-二甲基吡唑-1-基）-1,1-二苯乙基] -1,3-环戊二烯（1a）和2- [2 ，2-双（3,5-二甲基吡唑-1-基）-1,1-二苯乙基] -1,3-环戊二烯（1b））和bpztcpH（1- [2,2-双（3,5-二甲基吡唑- 1-基）-1-叔丁基乙基] -1,3-环戊二烯（2a）和2- [2,2-双（3,5-二甲基吡唑-1-基）-1-叔丁基乙基] -1， 3-环戊二烯（图2b）） -是由双（3,5-二甲基吡唑-1-基）甲烷与卜的去质子化制备ñ李接着反应用6,6- diphenylfulvene或6-叔-丁基富烯和随后用饱和氯化铵水溶液处理。蝎子/环戊二烯杂化物与[M（CH 2 SiMe 3）3（THF）3 ]（M = Sc，Y）的反应得到二烷基络合物[M（CH 2 SiMe 3）2（bpzcp）]（M = Sc （3），Y（4））和[M（CH