(2-((2,6-diethylphenyl)amido)-4-((2,6-diethylphenyl)imino)-2-pentene)ZnN(SiMe3)2 | 340026-16-6

• 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: (2-((2,6-diethylphenyl)amido)-4-((2,6-diethylphenyl)imino)-2-pentene)ZnN(SiMe3)2
• 英文别名: (BDI')ZnN(TMS)2；[(2-((2,6-diethylphenyl)amido)-4-((2,6-diethylphenyl)imino)-2-penteneato)ZnN(SiMe3)2]；[(2-((2,6-diethylphenyl)amido)-4-((2,6-diethylphenyl)imino)-2-pentene)ZnN(SiMe3)2]
• CAS: 340026-16-6
• 化学式: C₃₁H₅₁N₃Si₂Zn
• 分子量: 587.327
• InChiKey: ZLSWATUOCQCVHR-XOSYCPCOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  乳酸甲酯 、 (2-((2,6-diethylphenyl)amido)-4-((2,6-diethylphenyl)imino)-2-pentene)ZnN(SiMe3)2 以 甲苯 为溶剂， 以48%的产率得到rac-[(2-((2,6-diethylphenyl)amido)-4-((2,6-diethylphenyl)imino)-2-pentene)Zn(CH(CH3)CO2CH3)]2
  参考文献：
  名称：

  Single-Site β-Diiminate Zinc Catalysts for the Ring-Opening Polymerization of β-Butyrolactone and β-Valerolactone to Poly(3-hydroxyalkanoates)

  摘要：

  Polymerization of beta-butyrolactone (BBL) and beta-valerolactone (BVL) using the zinc alkoxide initiator (BDI-1)(ZnOPr)-Pr-l [(BDI-1) = 2-((2,6-diisopropylphenyl)amido)-4-((2,6-diisopropylphenyl)imino)-2-pentene] proceeds very rapidly under mild conditions to produce poly(3-hydroxybutyrate) (PHB) and poly(3-hyd roxyvalerate) (PHV), respectively. For the monomer-to-initiator ratio 200:1, PHB number-average molecular weights (M-n) are proportional to conversion throughout the reaction and polydispersity indices (PDIs) are narrow, consistent with a living polymerization. Higher monomer-to-initiator ratios can be used to achieve high molecular weight PHB (Mn > 100 000). End-group analysis verifies that the polymerization of BBL follows a coordination-insertion mechanism, where complexes of the form (BDI-1)ZnOCH(Me)CH2CO2R are the active species. Variable temperature NMR experiments show that (BDI-1)ZnO/Pr is monomeric in benzene-d(6) solution. In contrast, (BDI-2)ZnO/Pr [(BDI-2) = 2-((2,6-diethylphenyl)amido)-4-((2,6-diethy[phenyl)imino)-2-pentene] is a poor initiator at room temperature because it prefers to form a bis-mu-isopropoxide dimer in solution. According to kinetic studies, propagation by (BDI-1)ZnO/Pr is first order in both monomer as well as (BDI-1)ZnO/Pr concentration. These results lead us to propose a monometallic active species. Several results suggest that elimination side reactions are slowly catalyzed by zinc alkoxides, leading to degradation of the polymer.

  DOI：

  10.1021/ja020978r
• 作为产物：
  描述：

  bis(bis(trimethylsilyl)amido)zinc(II) 、 2-((2,6-diethylphenyl)amido)-4-((2,6-diethylphenyl)imino)-2-pentene 以 甲苯 为溶剂， 以62%的产率得到(2-((2,6-diethylphenyl)amido)-4-((2,6-diethylphenyl)imino)-2-pentene)ZnN(SiMe3)2
  参考文献：
  名称：

  丙交酯与锌和镁 β-二亚胺配合物的聚合：立体控制和机理

  摘要：

  已经制备了一系列基于 β-二亚胺配体框架的锌 (II) 和镁 (II) 醇盐。[(BDI-1)ZnO(i)Pr](2) [(BDI-1) = 2-((2,6-二异丙基苯基)酰胺基)-4-((2,6-二异丙基苯基)亚氨基)-2-戊烯] 在研究外消旋和内消旋丙交酯聚合成聚乳酸 (PLA) 的锌配合物中表现出最高的活性和立体选择性。[(BDI-1)ZnO(i)()Pr](2) 将 (S,S)-丙交酯聚合成全同立构 PLA，没有单体差向异构化，外消旋丙交酯变成异同立构 PLA (P(r) = 0.94 at 0° C)，以及内消旋丙交酯到间规 PLA（P(r) = 0.76 在 0 摄氏度）。除了数均分子量与转化率曲线和单体与催化剂比率的线性性质外，聚合反应是活跃的，这由分离的聚合物的窄多分散性证明。β-二亚胺配体上的取代基对聚合过程产生显着影响，影响立体选择性程度和聚合速率。[(BDI-1)ZnO(i)Pr](2)

  DOI：

  10.1021/ja003851f
• 作为试剂：
  描述：

  丁二酸酐 、 紫杉醇 在 (2-((2,6-diethylphenyl)amido)-4-((2,6-diethylphenyl)imino)-2-pentene)ZnN(SiMe3)2 作用下， 以 四氢呋喃 为溶剂， 反应 4.33h， 以55.4%的产率得到2',7-disuccinyltaxol
  参考文献：
  名称：

  Drug-Initiated, Controlled Ring-Opening Polymerization for the Synthesis of Polymer–Drug Conjugates

  摘要：

  Paclitaxel, a polyol chemotherapeutic agent, was covalently conjugated through its 2'-OH to polylactide with 100% regioselectivity via controlled polymerization of lactide mediated by paclitaxel/(BDI-II)ZnN(TMS)(2) (BDI-II = 2-((2,6-diisopropylphenyl)amino)-4-((2,6-diisopropylphenyl)imino)-2-pentene). The steric bulk of the substituents on the N-aryl groups of the BDI ligand drastically affected the regiochemistry of coordination of the metal catalysts to paclitaxel and the subsequent ring-opening polymerization of lactide. The drug-initiated, controlled polymerization of lactide was extended, again with 100% regioselectivity, to docetaxel, a chemotherapeutic agent that is even more structurally complex than paclitaxel. Regioselective incorporation of paclitaxel (or docetaxel) to other biopolymers (i.e., poly(delta-valerolactone), poly(trimethylene carbonate), and poly(epsilon-caprolactone)) was also achieved through drug/(BDI-II)ZnN(TMS)(2)-mediated controlled polymerization. These drug-polylactide conjugates with precisely controlled structures are expected to be excellent building blocks for drug delivery, coating, and controlled-release applications.

  DOI：

  10.1021/ma202581d

文献信息

• Single-Site β-Diiminate Zinc Catalysts for the Alternating Copolymerization of CO₂ and Epoxides:  Catalyst Synthesis and Unprecedented Polymerization Activity
  作者：Ming Cheng、David R. Moore、Joseph J. Reczek、Bradley M. Chamberlain、Emil B. Lobkovsky、Geoffrey W. Coates

  DOI：10.1021/ja003850n

  日期：2001.9.1

  Synthetic routes to zinc ss -diiminate complexes are reported. The synthesis of 11 ss -diimine [(BDI)H] ligands, with varying N-aryl substituents and bridging structures, is described. These ligands are converted to (BDI)ZnX complexes (X = OAc. Et. N(SiMe3)(2), Br, Cl, OH, OMe, (OPr)-Pr-i). X-ray structural data revealed that all zinc complexes examined exist as mu -X-bridged dimers in the solid state, with the exception of the zinc ethyl and amido complexes which were monomeric. Complexes of the form (BDI)ZnOR (R = alkyl, acyl) and (BDI)ZnN(SiMe3)(2) are highly active catalysts for the alternating copolymerization of epoxides and CO2. Copolymerizations of cyclohexene oxide (CHO) and CO2 with (BDI-1)ZnX [(BDI-1) = 2-((2,6-diisopropylphenyl)amido)-4-((2,6-diisopropylphenyl)imino)-2-pentene)] and (BDI-2)ZnX [(BDI-2) = 2-((2,6-diethylphenyl)amido)-4-((2,6-diethylphenyl)imino)-2-pentene)], where X = OAc, Et, N(SiMe3)(2), Br, Cl, OH, OMe, (OPr)-Pr-i, were attempted at 50 degreesC and 100 Psi CO2. Complexes with X = OAc, N(SiMe3)(2), OMe, (OPr)-Pr-i all produced polycarbonate by the alternated insertion of CHO and CO2 with similar catalytic activities, comparable molecular weights, and narrow molecular weight distributions (MWD similar to 1.1), indicating the copolymerizations are living. Furthermore, ligand effects were shown to dramatically influence the polymerization activity as minor steric changes accelerated or terminated the polymerization activity.
• Mechanism of the Alternating Copolymerization of Epoxides and CO₂ Using <i>β</i>-Diiminate Zinc Catalysts:  Evidence for a Bimetallic Epoxide Enchainment
  作者：David R. Moore、Ming Cheng、Emil B. Lobkovsky、Geoffrey W. Coates

  DOI：10.1021/ja030085e

  日期：2003.10.1

  A series of zinc beta-diiminate (BDI) complexes and their solid-state structures, solution dynamics, and copolymerization behavior with CO2 and cyclohexene oxide (CHO) are reported. Stoichiometric reactions of the copolymerization initiation steps show that zinc alkoxide and bis(trimethylsilyl)amido complexes insert CO2, whereas zinc acetates react with CHO. [(BDl-2)ZnOMe](2) [(BDI-2) = 2-((2,6-diethylphenyl)amido)-4-((2,6-diethylphenyl)imino)-2-pentene] and (BDI-1)(ZnOPr)-Pr-i [(BDI-1) = 2-((2,6-diisopropylphenyl)amido)-4-((2,6-diisopropylphenyl)imino)-2-pentene] react with CO2 to form [(BDI-2)Zn(mu-OMe) (mu,eta(2)-O2COMe)Zn(BDI-2)] and [(BDI-1)Zn(mu-eta(2)-(O2COPr)-Pr-i)](2), respectively. (BDI-2)ZnN(SiMe3)(2) inserts CO2 and eliminates trimethylsilyl isocyanate to give [(BDI-2)Zn(mu-OSiMe3)](2). [(BDI-7)Zn(mu-OAc)](2) [(BDI-7) = 3-cyano-2-((2,6-diethylphenyl) amido)-4-((2,6-diethylphenyl)imino)-2-pentene) reacts with 1.0 equiv of CHO to yield [(BDI-7)Zn(mu,eta(2)-OAc)-(mu,eta(1)-OCyOAc)Zn(BDI-7)]. Under typical polymerization conditions, rate studies on the copolymerization exhibit no dependence in [CO2], a first-order dependence in [CHO], and orders in [Zn]tot ranging from 1.0 to 1.8 for [(BDI)ZnOAc] complexes. The copolymerizations of CHO (1.98 M in toluene) and 300 Psi CO2 at 50 degreesC using [(BDI-1)ZnOAc] and [(BDI-2)ZnOAc] show orders in [Zn](tot) of 1.73 +/- 0.06 and 1.02 +/- 0.03, respectively. We propose that two zinc complexes are involved in the transition state of the epoxide ring-opening event.