| 530135-33-2

• CAS: 530135-33-2
• 化学式: C₃₇H₅₅AlN₂O₂
• 分子量: 586.837
• InChiKey: IOCOZGOIIDMNNG-SEILFYAJSA-L

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：

  叔丁基二甲基硅烷醇 、 以 甲苯 为溶剂， 以97%的产率得到(R,R)-[t-Bu-Salcyen]AlOSi-t-BuMe2
  参考文献：
  名称：

  Phospho-Aldol Catalysis via Chiral Schiff Base Complexes of Aluminum

  摘要：

  Chiral complexes of aluminum containing the salcyen ligand framework, [(R,R)-salcyen]-AIX (X = Me, (OSiMe2Bu)-Bu-t), catalyze the asymmetric addition of diorgano-H-phosphonates to carbonyls: the phospho-aldol reaction. Reaction proceeds smoothly at ambient temperature in various solvents and under aerobic conditions, to afford alpha -hydroxyphosphonate esters (MeO)(2)P(O)CHR(OH), with enantiomeric excesses (ee's) <50%. Although catalyst activity is linked to the nature of X, ee's appear to be only slightly affected. Substitution within the chiral salcyen ligand framework seems to affect ee principally where there is a steric or structural change near the metal center. Although catalysis is tolerant of small quantities of water, excess water leads to attenuation of enantioselectivity through decomposition of catalyst to afford hydrated aluminas which competes through achiral phospho-aldol catalysis. Kinetic analyses reveal a second-order polynomial relationship of the form x/([A(0)] - x)-[A(0)] = k(2)t + k(2)t(2), where [A(0)] is the initial concentration of H-phosphonate and carbonyl and x the degree of reaction. This may suggest that the metal complex must first be converted to another, more active precursor prior to catalytic turnover. Hammett analyses suggest that carbonyl binding to the metal center results in enhanced ee's, while single-crystal analyses on four aluminum complexes support the view that twisting of the ligand framework, as measured by the five-coordinate parameter, from a purely meridional geometry may be advantageous to stereoselectivity. Strategies for future developments are discussed in light of the results herein.

  DOI：

  10.1021/om000386m
• 作为产物：
  描述：

  3,5-二叔丁基水杨醛 以 乙醇 、 正己烷 、 甲苯 为溶剂， 反应 8.0h， 生成
  参考文献：
  名称：

  铝催化二硫内酯开环聚合制备具有性能优势的立规可回收塑料

  摘要：

  铝络合物与硫化物增长物质具有适当的结合亲和力，可避免催化剂中毒并最大限度地减少差向异构化反应。通过适当的配体设计和修饰，铝催化剂能够生产高度全同立构的立体络合聚硫酯。获得的二硫内酯基塑料是一种坚韧的半结晶材料，具有完全的可回收性。

  DOI：

  10.1002/anie.202302898
• 作为试剂：
  描述：

  1-异苯甲腈 、 环己烷基甲醛 在 迭氮酸 、 (R,R)-[Salen-t-Bu]AlMe 作用下， 以 甲苯 为溶剂， 以68%的产率得到cyclohexyl(1-phenyl-1H-tetrazol-5-yl)methanol
  参考文献：
  名称：

  通过催化对映选择性Passerini型反应不对称合成5-（1-羟烷基）四唑。

  摘要：

  DOI：

  10.1002/anie.200804213

文献信息

• Dual Catalyst System for Asymmetric Alternating Copolymerization of Carbon Dioxide and Cyclohexene Oxide with Chiral Aluminum Complexes: Lewis Base as Catalyst Activator and Lewis Acid as Monomer Activator
  作者：Kiyoshi Nishioka、Hidetoshi Goto、Hiroshi Sugimoto

  DOI：10.1021/ma301696d

  日期：2012.10.23

  Optically active aluminum complexes such as Schiff base, binuclear β-ketoiminate, and bisprolinol complexes were found to promote asymmetric alternating copolymerizations of carbon dioxide and cyclohexene oxide. The aluminum Schiff base complexes–tetraethylammonium acetate afforded isotactic poly(cyclohexene carbonate)s with low enantioselectivities. Lewis bases having two coordinating sites were utilized

  发现光学活性铝络合物，例如席夫碱，双核β-酮亚胺酸盐和双脯氨醇络合物可促进二氧化碳和环己烯氧化物的不对称交替共聚。铝席夫碱配​​合物乙酸四乙铵可提供低对映选择性的全同立构聚碳酸环己烯酯。基于通过X射线晶体学澄清的β-酮亚胺化铝的双核结构，利用具有两个配位位点的路易斯碱来增强活性和选择性。[ 2克AlMe] 2–庞大的联咪唑制得了具有高对映选择性（62％ee）的交替共聚物。由于笨重的路易斯碱与铝在较少的对映选择性位点上的配位，认为聚合反应优先在较拥挤的对映选择性位点进行。3 2 AlMe–2-甲基吡啶也表现出高对映选择性（67％ee）。甲基铝双（2,6-二叔丁基-4-甲基苯酚）用于在低温下（82％ee）进行更快，更对映选择性的共聚。发现不对称共聚反应显着取决于环氧化物的大小，温度和活化剂的种类/量。