1-[2,2-bis(3,5-dimethylpyrazol-1-yl)-1-phenylethyl]-1,3-cyclopentadiene | 948037-65-8

• 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: 1-[2,2-bis(3,5-dimethylpyrazol-1-yl)-1-phenylethyl]-1,3-cyclopentadiene
• 英文别名: 1-[(2R)-2-cyclopenta-1,3-dien-1-yl-1-(3,5-dimethylpyrazol-1-yl)-2-phenylethyl]-3,5-dimethylpyrazole
• CAS: 948037-65-8
• 化学式: C₂₃H₂₆N₄
• 分子量: 358.486
• InChiKey: IQFSJOSBVZNUTE-QFIPXVFZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.9
• 重原子数：
  27
• 可旋转键数：
  5
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.3
• 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-phenylethyl]-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91%的产率得到[Mg(CH₂SiMe₃)(κ²-η⁵-bpzpcp)]
  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

• Expanding Heteroscorpionates. Facile Synthesis of New Hybrid Scorpionate/Cyclopentadienyl Ligands and Their Lithium and Group 4 Metal Compounds:  A Combined Experimental and Density Functional Theory Study
  作者：Antonio Otero、Juan Fernández-Baeza、Antonio Antiñolo、Juan Tejeda、Agustín Lara-Sánchez、Luis F. Sánchez-Barba、Margarita Sánchez-Molina、Ana M. Rodríguez、Carles Bo、Manuel Urbano-Cuadrado

  DOI：10.1021/om7003942

  日期：2007.8.1

  The preparation of new hybrid scorpionate/cyclopentadienyl ligands in the form of the lithium derivatives [Li(bpzcp)(THF)] (1) [bpzcp = 2,2-bis(3,5-dimethylpyrazol-1-yl)-1,1-diphenylethylcyclopentadienyl] and [Li(bpztcp)(THF)] (2) [bpztcp = 2,2-bis(3,5-dimethylpyrazol-1-yl)-1-tert-butylethylcyclopentadienyl] or as a mixture of the two scorpionate/cyclopentadiene regioisomers (bpzpcpH) 1-[2,2-bis(3

  以锂衍生物[Li（bpzcp）（THF）]（1）[bpzcp = 2,2-双（3,5-二甲基吡唑-1-基）-1， 1-二苯基乙基环戊二烯基]和[Li（bpztcp）（THF）]（2）[bpztcp = 2,2-双（3,5-二甲基吡唑-1-基）-1-叔丁基乙基环戊二烯基]或两者的混合物蝎子酸酯/环戊二烯区域异构体（bpzpcpH）1- [2,2-双（3,5-二甲基吡唑-1-基）-1-苯乙基] -1,3-环戊二烯（3a）和2- [2,2-bis（通过双（3,5-二甲基吡唑-1-基）甲烷（bdmpzm）与Bu n的反应，进行了3​​,5-二甲基吡唑-1-基）-1-苯基乙基]，3-环戊二烯（3b）的反应。Li和6-叔丁基的6,6-二苯基富烯-丁基富勒烯或6-苯基富勒烯。然而，当用6，6-二甲基富勒烯进行该插入反应时，获得化合物[Li（isopr cp）（bdmpzm）（THF）]（4）[ isopr