rac-2,2'-bis(3-t-butyl-2-hydroxybenzylideneimine)1,1'-binaphthyl | 138937-09-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: rac-2,2'-bis(3-t-butyl-2-hydroxybenzylideneimine)1,1'-binaphthyl
• 英文别名: 2,2'-bis((3-tert-bytyl-2-hydroxybenzylidene)amino)-1,1'-binaphthyl；2,2'-bis[(3-tert-butyl-2-hydroxybenzylidene)amino]-1,1'-binaphthyl；2-Tert-butyl-6-[[1-[2-[(3-tert-butyl-2-hydroxyphenyl)methylideneamino]naphthalen-1-yl]naphthalen-2-yl]iminomethyl]phenol
• CAS: 138937-09-4；232266-04-5；192387-47-6
• 化学式: C₄₂H₄₀N₂O₂
• 分子量: 604.792
• InChiKey: ITERUMNXUVYAIH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  11.3
• 重原子数：
  46
• 可旋转键数：
  7
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.19
• 拓扑面积：
  65.2
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  titanium(IV) isopropylate 、 rac-2,2'-bis(3-t-butyl-2-hydroxybenzylideneimine)1,1'-binaphthyl 以 甲苯 为溶剂， 反应 24.0h， 以62%的产率得到
  参考文献：
  名称：

  Synthesis, structure, and catalytic activity of titanium complexes with chiral biaryl Schiff-base ligands

  摘要：

  A series of chiral organo-titanium complexes have been prepared from the reaction between Ti((OPr)-Pr-i)(4) and chiral biaryl Schiff-base ligands 1H(2)-12H. The steric demand of the ligand plays an important role in the formation of the titanium complexes. For example, treatment of ligand 1H(2) with 1 equiv of Ti((OPr)-Pr-i)(4) in toluene at room temperature gives, after recrystallization from a toluene solution, the chiral bis-ligated titanium complex (L1)(2)Ti (14). While under similar reaction conditions, the more bulky ligands 2H(2), 4H(2), and 6H(2) form the mono-ligated titanium complexes (L2)Ti((OPr)-Pr-i)(2) (15), (L4)Ti((OPr)-Pr-i)(2)(19), and (L6)Ti((OPr)-Pr-i)(2) (22), respectively, in good yields. The mono-ligated titanium alkoxides can be converted to bis-ligated complex via ligand redistribution reaction. For one instance, treatment of mono-ligated complex (L2)Ti((OPr)-Pr-i)(2) (15) in benzene at 60 degrees C results in the isolation of the bis-ligated complex (L2)(2)Ti (16) in 92% yield. All titanium complexes have been characterized by various spectroscopic techniques and elemental analyses. The solid-state structures of complexes 14-21, 23, 24 and 29 have further been confirmed by X-ray diffraction analyses. The titanium complexes are active catalysts for the asymmetric hydrophosphonylation of aromatic aldehydes with moderate enantioselectivities. (C) 2013 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.ica.2013.04.008
• 作为产物：
  描述：

  3-叔丁基-2-羟基苯甲醛 、 [1,1’-联萘]-2,2’-二胺 以 甲苯 为溶剂， 以98%的产率得到rac-2,2'-bis(3-t-butyl-2-hydroxybenzylideneimine)1,1'-binaphthyl
  参考文献：
  名称：

  含双和四齿水杨醛亚胺衍生物的 MAO 活化的二氯钛配合物的乙烯聚合行为

  摘要：

  以高产率合成了带有二甲基联苯 (1-Ti-3-Ti) 的新型手性桥连四齿 (N 2 O 2 )Ti IV Cl 2 型配合物和先前公布的联萘桥连 (4-Ti) 配合物。这是通过用Ti(NMe 2 ) 4 处理相应的席夫碱配体(H 2 L) 前体，然后通过添加过量的Me 3 -SiCl 将这些二酰氨基络合物转化为LTiCl 2 衍生物来实现的。研究了一系列在苯氧基具有相似取代基的未桥连钛配合物 5-Ti-8-Ti，并与上述桥连配合物进行了比较，并在甲基铝氧烷 (MAO) 活化后研究了它们的聚合性能。发现带有手性四齿联芳基桥联水杨醛亚胺配体的催化剂产生低活性 [低于 10 kg PE /(mol Ti hbar)] 的多峰聚乙烯 (PE) 而它们的未桥连类似物在类似条件下提供 10-1000 倍的活性反应条件。基于不同阳离子物种构型的稳定性讨论了聚合活性存在这种巨大差异的原因。

  DOI：

  10.1002/ejic.200900840
• 作为试剂：
  描述：

  2-isothiocyanatopropionic acid methyl ester 、 苯乙酮 在 rac-2,2'-bis(3-t-butyl-2-hydroxybenzylideneimine)1,1'-binaphthyl 、 二丁基镁 作用下， 以 四氢呋喃 为溶剂， 反应 43.0h， 生成 (4R,5R)-methyl 4,5-dimethyl-5-phenyl-2-thioxooxazolidine-4-carboxylate 、
  参考文献：
  名称：

  通过直接催化不对称醛醇和曼尼希型反应构建连续的四取代手性碳立体中心

  摘要：

  描述了具有邻位四取代的手性碳立体中心的非天然氨基酸的催化不对称合成。在第一部分中，实现了简单的未活化的酮亲电体与α-取代的α-异硫氰酸酯供体的直接催化不对称醛醇缩合反应。镁/席夫碱催化剂促进了醛醇缩合反应，在高达98％ee和98：2 dr的条件下获得了α-氨基-β-羟基酯。第二部分，镁/席夫碱催化剂和Sr /席夫碱催化剂用于酮亚胺的立体发散性直接不对称曼尼希型反应。Mg / Schiff碱催化剂产生合成α-β-二氨基酯，而Sr / Schiff碱催化剂产生抗α-β-二氨基酯，对映选择性高至高，对比例高达97％ee。DOI 10.1002 / tcr.201100020

  DOI：

  10.1002/tcr.201100020

文献信息

• Synthesis and catalytic activity of group 5 metal amides with chiral biaryldiamine-based ligands
  作者：Furen Zhang、Haibin Song、Guofu Zi

  DOI：10.1039/c0dt01229g

  日期：——

  6′-dimethyl-1,1′-biphenyl (6H2), (R)-2,2′-bis[(3,5-di-tert-butyl-2-hydroxybenzylidene)amino]-6,6′-dimethyl-1,1′-biphenyl (7H2), (R)-2,2′-bis[(3-tert-butyl-2-hydroxybenzylidene)amino]-1,1′-binaphthyl (8H2), (S)-2-(mesitoylamino)-2′-(dimethylamino)-1,1′-binaphthyl (9H), and (R)-2-(mesitoylamino)-2′-(dimethylamino)-6,6′-dimethyl-1,1′-biphenyl (10H), which are derived from (R) or (S)-2,2′-diamino-1,1′-binaphthyl

  从V（NMe 2）4或M（NMe 2）5（M = Nb，Ta）与手性配体（R）-2,2'-bis（甲磺酰氨基）-1,1'-联萘（1 H 2），（R）-5,5'，6,6'，7,7'，8,8'-八氢-2,2'-双（甲磺酰氨基） -1,1'-联萘基（2 H 2），（R）-6,6'-二甲基-2,2'-双（甲磺酰氨基）-1,1'-联苯（3 H 2），（R）- 2,2'-双（均三甲磺酰基氨基）-6,6'-二甲基-1,1'-联苯（4 H 2），（R）-2,2'-双（二苯基硫代磷氨基）-1,1'-联萘基（5 H 2），（R）-2,2'-双[（3-叔丁基-2-羟基亚苄基）氨基] -6 ，6'-二甲基-1,1'-联苯（6 H 2），（R）-2,2'-双[（3,5-二叔丁基-2-羟基苄叉基）氨基] -6,6 ′-二甲基-1,1'-联苯（7 H 2），（R）-2,2'-双[（3-叔丁基-2-羟基亚苄基）氨基] -1
• Pairing-Enhanced Regioselectivity: Synthesis of Alternating Poly(lactic-<i>co</i>-glycolic acid) from Racemic Methyl-Glycolide
  作者：Yiye Lu、Geoffrey W. Coates

  DOI：10.1021/jacs.3c05941

  日期：2023.10.18

  established the synthesis of isotactic, alternating PLGA from enantiopure starting materials. Here, to fill in the gap of the current field, we have developed the synthesis of syndioenriched, alternating PLGA from racemic methyl-glycolide (rac-MeG). The synthesis of alternating PLGA is accomplished by a highly regioselective ring-opening polymerization of rac-MeG with an optimized racemic aluminum catalyst

  聚乳酸乙醇酸(PLGA)在体内用于各种生物医学应用。由于其生物降解性和生物相容性，PLGA 特别适合肠胃外给药的受控药物输送。此前，我们建立了从对映体纯起始材料合成全同立构、交替 PLGA 的方法。在这里，为了填补当前领域的空白，我们开发了从外消旋甲基乙交酯（rac-MeG ）合成间二富集的交替PLGA的方法。交替PLGA的合成是通过外消旋-MeG与优化的外消旋铝催化剂的高度区域选择性开环聚合来完成的。进行机理研究以阐明配对增强催化剂的区域控制和立体控制。聚合物序列保真度已通过核磁共振研究确定，证实了主链立体构型内共聚单体序列的高度交替和中等的间同立构规整度。所得间二富集材料是无定形的，这将有利于药物络合行为。
• Polymerization of ethylene and propene promoted by binaphthyl-bridged Schiff base complexes of titanium
  作者：Maria Strianese、Marina Lamberti、Mina Mazzeo、Consiglia Tedesco、Claudio Pellecchia

  DOI：10.1016/j.molcata.2006.05.046

  日期：2006.10

  Three new binaphthyl-bridged Schiff base complexes featuring different phenolate substituents (meta-Me, orthopara-di-Cl, orthopara-di-Br) were synthesized. H-1 and C-13 NMR analyses indicated that the cis-beta isomers are preferentially formed in any case. These complexes were tested as precatalysts for ethylene and propene polymerization comparing their behaviour to that of related titanium and zirconium complexes previously reported.The beneficial effect on polymerization activity of halogen atoms in the ortho, para positions of the phenolate rings was also demonstrated. (c) 2006 Elsevier B.V. All rights reserved.
• Synthesis, crystal structure and application in regio- and stereoselective epoxidation of allylic alcohols of a titanium binaphthyl-bridged Schiff base complex
  作者：Annunziata Soriente、Margherita De Rosa、Marina Lamberti、Consiglia Tedesco、Arrigo Scettri、Claudio Pellecchia

  DOI：10.1016/j.molcata.2005.03.012

  日期：2005.7

  A new octahedral titanium binaphthyl-bridged Schiff base complex (1) was synthesized and characterized. Analysis by H-1 and C-13-NMR spectroscopy and X-ray crystallography indicated that the C-1-symmetric cis-beta isomer is preferentially formed as one of the two possible enantiomeric couples of diasteroisomers. The catalytic behaviour of the complex 1 toward epoxidation of allylic alcohols was investigated. Using only 0.5% mol of the complex 1 the epoxyalcohols are obtained in very high regio-, chemo- and diastercoselctive way by the MW exposure of the mixture in solvent free-conditions. (c) 2005 Elsevier B.V. All rights reserved.