[(4R,5R)-2,2-dimethyl-α,α,α',α'-tetraphenyl-1,3-dioxolane-4,5-dimethanolato-O,O']dichlorotitanium(IV)

• 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: [(4R,5R)-2,2-dimethyl-α,α,α',α'-tetraphenyl-1,3-dioxolane-4,5-dimethanolato-O,O']dichlorotitanium(IV)
• 英文别名: dichloro-(R,R-4,5-bis(diphenyloxymethyl)-2,2-dimethyl-1,3-dioxane)titanium(IV)；TiCl2((4R,5R)-2,2-dimethyl-α,α,α',α'-tetraphenyl-1,3-dioxolane-4,5-dimethanol(-2H))；titanium((4R,5R)-2,2-dimethyl-α,α,α',α'-tetraphenyl-1,3-dioxolane-4,5-dimethylate)Cl2；[(4R,5R)-2,2-dimethyl-5-[oxido(diphenyl)methyl]-1,3-dioxolan-4-yl]-diphenylmethanolate;titanium(4+);dichloride
• 化学式: C₃₁H₂₈Cl₂O₄Ti
• 分子量: 583.347
• InChiKey: HMHIUCHGZIYPAH-CRMRIEQBSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  -1.88
• 重原子数：
  38
• 可旋转键数：
  6
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.23
• 拓扑面积：
  64.6
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  [(4R,5R)-2,2-dimethyl-α,α,α',α'-tetraphenyl-1,3-dioxolane-4,5-dimethanolato-O,O']dichlorotitanium(IV) 、 甲基锂 以 甲苯 为溶剂， 生成
  参考文献：
  名称：

  TADDOLate钛（IV）配合物介导的烯烃的不对称Kulinkovich羟基丙烷化反应

  摘要：

  专用于奥列格Kulinkovich教授在他的70之际个生日 抽象的 据报道羧酸酯与前手性烯烃不对称的库林科维奇环丙烷化。该过程由钛（IV）（4 R，5 R）-TADDOLate络合物介导，如果存在分子内或分子间烯烃配体，则可提供相应的（Z）-或（E）-环丙醇，ee最高可达84-87％中间的钛环丙烷[钛（II）-烯烃]中进行交换。烯烃双键的构型保留在环丙烷产品中，指出在环丙烷形成步骤中Ti-C键的构型完全保留。该结果已在食盐复杂机制的框架内得到解释，表明形成五配位钛酸盐物种是高度对映体控制的先决条件。 据报道羧酸酯与前手性烯烃不对称的库林科维奇环丙烷化。该过程由钛（IV）（4 R，5 R）-TADDOLate络合物介导，如果存在分子内或分子间烯烃配体，则可提供相应的（Z）-或（E）-环丙醇，ee最高可达84-87％中间的钛环丙烷[钛（II）-烯烃]中进行交换。烯烃双键的构型保留在环丙烷产品中

  DOI：

  10.1055/s-0037-1611709
• 作为产物：
  描述：

  bis{(4R,5R)-2,2-dimethyl-α,α,α',α'-tetraphenyl-1,3-dioxolane-4,5-dimethanolato-O,O'}titanium(IV) 、 四氯化钛 以 甲苯 为溶剂， 生成 [(4R,5R)-2,2-dimethyl-α,α,α',α'-tetraphenyl-1,3-dioxolane-4,5-dimethanolato-O,O']dichlorotitanium(IV)
  参考文献：
  名称：

  TADDOLate钛（IV）配合物介导的烯烃的不对称Kulinkovich羟基丙烷化反应

  摘要：

  专用于奥列格Kulinkovich教授在他的70之际个生日 抽象的 据报道羧酸酯与前手性烯烃不对称的库林科维奇环丙烷化。该过程由钛（IV）（4 R，5 R）-TADDOLate络合物介导，如果存在分子内或分子间烯烃配体，则可提供相应的（Z）-或（E）-环丙醇，ee最高可达84-87％中间的钛环丙烷[钛（II）-烯烃]中进行交换。烯烃双键的构型保留在环丙烷产品中，指出在环丙烷形成步骤中Ti-C键的构型完全保留。该结果已在食盐复杂机制的框架内得到解释，表明形成五配位钛酸盐物种是高度对映体控制的先决条件。 据报道羧酸酯与前手性烯烃不对称的库林科维奇环丙烷化。该过程由钛（IV）（4 R，5 R）-TADDOLate络合物介导，如果存在分子内或分子间烯烃配体，则可提供相应的（Z）-或（E）-环丙醇，ee最高可达84-87％中间的钛环丙烷[钛（II）-烯烃]中进行交换。烯烃双键的构型保留在环丙烷产品中

  DOI：

  10.1055/s-0037-1611709
• 作为试剂：
  描述：

  反式硝基苯乙烯 、 1-环己烯氧基三甲基硅烷 在 [(4R,5R)-2,2-dimethyl-α,α,α',α'-tetraphenyl-1,3-dioxolane-4,5-dimethanolato-O,O']dichlorotitanium(IV) 、 氟化铵 作用下， 以 甲苯 、 甲醇 为溶剂， 反应 24.0h， 以88%的产率得到(S)-2-[(R)-2-nitro-1-phenylethyl]cyclohexanone
  参考文献：
  名称：

  Dichloro[TADDOLato(2−)‐ O , O ′]titanium/Dichlorobis[1‐methylethoxy]titanium‐Mediated, Highly Diastereo‐ and Enantioselective Additions of Silyl Enol Ethers to Nitro Olefins and [3+2] Cycloadditions of Primary Adducts to Acetylenes

  摘要：

  The diastereoselective, Ti-Lewis-acid-mediated, low-temperature addition of silyl enol ethers to 1-aryl-2-nitroethenes (Scheme 1) occurs enantioselectively with dichloro[TADDOLato(2-)-O,O']titanium 3 (TADDOL = alpha,alpha,alpha',alpha'-tetraaryl-1,3-dioxolane-4,5-dimethanol) (Scheme 2). At least 3 equiv. of Lewis acid are required for high conversions (yields). However, the chiral Lewis acid 3 can be 'diluted' with the achiral Cl2Ti(OCHMe2)(2) analog (ratio 1:2.5), with hardly any loss of enantioselectivity! Both, the primary (4 + 2) cycloadducts(B, 9) and the gamma-nitro ketones (A, la-h, 5, 7),formed by hydrolysis, can be isolated in good yields and with high configurational purities (Schemes 3 and 4, and Table 1). The relative and absolute configurations (2S,1'R) of the products 1 from cyclohexanone silyl enol ether and 1-aryl(including 1-heteroaryl)-2-nitroethenes (obtained with (R,R)-TADDOLate) are assigned by NMR spectroscopy, and optical comparison and correlation with literature data, as well as by anomalous-dispersion X-ray crystal-structure determination (nitro ketone Ic: I;ig.). The nitro ketone 7 from cyclohex-2-enone and 4-methoxy-beta-nitrostyrene was cyclized (via a silyl nitronate C; Scheme 5) to the nitroso acetal 8, and one of the bicyclic nitronate primary adducts 9 underwent a [3 + 2] cycloaddition to phenylacetylene and to ethyl 2-butynoate to give, after a ring-contracting rearrangement, tricyclic aziridine derivatives with five consecutive stereocenters (10, 11; Scheme 5 and Table 2), in enantiomerically pure form. With an aliphatic nitro olefin. the Ti-TADDOLate-mediated reaction with (silyloxy)cyclohexene led to a moderate yield, but the product 4 was isolated in a high configurational purity.

  DOI：

  10.1002/(sici)1522-2675(19991110)82:11<1829::aid-hlca1829>3.0.co;2-#

文献信息

• Catalytic Asymmetric Cyclopropanation of Allylic Alcohols with Titanium-TADDOLate:  Scope of the Cyclopropanation Reaction
  作者：André B. Charette、Carmela Molinaro、Christian Brochu

  DOI：10.1021/ja0108382

  日期：2001.12.1

  titanium-TADDOLate complex was effective at catalyzing the cyclopropanation reaction of allylic alcohols in the presence 1 equiv of bis(iodomethyl)zinc. After initial optimization of the catalyst structure, excellent yields and enantiomeric ratios were obtained for 3-aryl- or 3-heteroaryl-substituted allylic alcohols (up to 97:3). Alkyl-substituted allylic alcohols gave modest yields and enantiomeric ratios (up

  在 1 当量的双（碘甲基）锌存在下，亚化学计量的钛-TADDOLate 络合物可有效催化烯丙醇的环丙烷化反应。在对催化剂结构进行初步优化后，3-芳基-或3-杂芳基-取代的烯丙醇（高达97:3）获得了优异的产率和对映体比率。烷基取代的烯丙醇的产率和对映体比例适中（高达 87:13），但与其他亚化学计量手性配体观察到的相比，这些更有利。本文介绍了该反应的完整合成范围。
• Titanium(IV) chloride complexes with chiral tetraaryl-1,3-dioxolane-4,5-dimethanol ligands as a new type of catalysts of ethylene polymerization
  作者：Yu. N. Belokon’、S. Ch. Gagieva、T. A. Sukhova、A. B. Dmitriev、K. A. Lyssenko、N. M. Bravaya、B. M. Bulychev、D. Seebach

  DOI：10.1007/s11172-006-0121-6

  日期：2005.10

  Titanium complexes of chiral ligands, (4R,5R)-2,2-dimethyl-α,α,α′,α′-tetraphenyl-1,3-dioxolane-4,5-dimethanol and its structural analogs, activated by polymethylalumoxane catalyze ethylene polymerization with an activity from 3 to 530 (kg polyethylene) (mol Ti h atm)−1. An increase in the bulk of the aryl substituents results in a decrease in the catalytic activity of the complexes.

  手性配体 (4R,5R)-2,2-二甲基-α,α,α′,α′-四苯基-1,3-二氧戊环-4,5-二甲醇及其结构类似物的钛配合物在聚甲基铝氧烷的活化下催化乙烯聚合，其活性从 3 到 530 (kg 聚乙烯) (mol Ti h atm)-1。芳基取代基数量的增加会导致配合物催化活性的降低。
• Titanium (IV) and zirconium (IV) chloride complexes on the base of chiral tetraaryl-1,3-dioxolane-4,5-dimetanol ligands in the polymerization of ethylene: The promoting role of lithium and magnesium chloride
  作者：Vladislav A. Tuskaev、Svetlana C. Gagieva、Victor I. Maleev、Alexandra O. Borissova、Mikhail V. Solov'ev、Zoya A. Starikova、Boris M. Bulychev

  DOI：10.1016/j.polymer.2013.06.041

  日期：2013.8

  Coordination compounds of titanium (IV) and zirconium (IV) with tetra-aryl-1,3-dioxolan-4,5-dimethanol (1,2) derivatives were synthesized and characterized by NMR- and IR-spectroscopy and X-ray crystallography. It was demonstrated that titanium dichloride complexes (5–6, 9–12) when treated with MAO, TMA or TIBA are inactive in ethylene polymerization catalysis. However, these compounds become catalytically

  合成了钛（IV）和锆（IV）与四芳基-1,3-二氧戊环-4,5-二甲醇（1,2）衍生物的配位化合物，并通过NMR和IR光谱以及X射线晶体学进行了表征。结果表明，二氯化钛配合物（5-6、9-12当用MAO处理时，TMA或TIBA在乙烯聚合催化中是惰性的。但是，这些化合物在氯化锂或氯化镁的存在下具有催化活性。已经发现，所得到的催化活性的大小与以下因素有关：将非过渡金属氯化物引入反应混合物的方式，活化剂的性质及其总量。产生的催化活性在54至3500 kg PE /摩尔Ti٠h٠bar之间变化。形成的聚合物是 具有高多分散指数的高和超高分子量（超过5.95 10 5 g / mol）的线性聚乙烯。提出了锂和镁氯化物促进催化过程的能力的可能机理。
• Insight into the Mechanism and Stereochemistry of the Transformations of Alkyltitanium Ate-Complexes. An Enhanced Enantioselectivity in the Cyclopropanation of the Carboxylic Esters with Titanacyclopropane Reagents
  作者：Oleg G. Kulinkovich、Dzmitry G. Kananovich、Margus Lopp、Victor Snieckus

  DOI：10.1002/adsc.201400480

  日期：2014.11.24

  AbstractThe dependence of the stereoselectivity of the cyclopropanation reaction of γ,γ‐diphenyl‐γ‐butyrolactone and carboxylic esters with alkylmagnesium bromides in the presence of titanium(IV) TADDOLates on the structure of the reactants has been examined in detail. It has been found that the enantioselectivity in the formation of cis‐1,2‐disubstituted cyclopropanols is a function of the structure of the carboxylic ester alkoxy group and leads, in the case of cyclopropanation of hexafluoroisopropyl alkanoates, to 84% ee. To rationalize these observations, as well as the NMR data on the structures of the TADDOL‐derived alkyltitanium species, a new mechanistic model for the formation of the five‐coordinated chiral titanacyclopropane reactive intermediates and their subsequent reorganization in the reactions with esters is proposed. The essential features of this model consist in the generation of configurationally stable TADDOL derived titanacyclopropane species with an apical or equatorial position of the stereogenic carbanion center which is followed by retention or inversion of absolute configuration in course of the displacement of the carboxylic ester alkoxy group.magnified image
• NARASAKA KOICHI; INOUE MASAYUKI; OKADA NAOKO, CHEM. LETT.,(1986) N 7, 1109-1112
  作者：NARASAKA KOICHI、 INOUE MASAYUKI、 OKADA NAOKO

  DOI：——

  日期：——