(4R,5R)-α,α,α',α'-tetraphenyl-2-phenyl-1,3-dioxolane-4,5-dimethanol | 130762-71-9

• 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)-α,α,α',α'-tetraphenyl-2-phenyl-1,3-dioxolane-4,5-dimethanol
• 英文别名: 2-[(4R,5R)-5-(2-hydroxypropan-2-yl)-2-phenyl-1,3-dioxolan-4-yl]propan-2-ol
• CAS: 130762-71-9
• 化学式: C₁₅H₂₂O₄
• 分子量: 266.337
• InChiKey: IVYGWWOMSVGNFS-VXGBXAGGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.01
• 重原子数：
  19.0
• 可旋转键数：
  3.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  58.92
• 氢给体数：
  2.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  titanium(IV) isopropylate 、 (4R,5R)-α,α,α',α'-tetraphenyl-2-phenyl-1,3-dioxolane-4,5-dimethanol 以 甲苯 为溶剂， 生成
  参考文献：
  名称：

  关于使用α，α，α'，α'-四芳基-1,3-二氧戊环-4,5-二甲醇（TADDOL）衍生的钛酸酯对映选择性反应的机理：C 2-和C 1对称TADDOLs之间的差异-事实，含义和概括†

  摘要：

  衍生自α，α，α'，α'-四芳基-1,3-二氧戊环-4,5-二甲醇（TADDOLs，由酒石酸盐制备）的钛酸酯用作二烷基锌化合物向醛的对映选择性加成的催化剂。对于为研究机理而选择的标准反应，即在苯甲醛中添加二乙基锌，TADDOLate配体上的不同芳基取代基的选择性变化很小（表2-4，示例）。0.02至0.2当量 对于手性钛酸酯，只有在过量的钛酸四异丙酯存在下才能观察到90％以上的选择性！根据NMR测量（图2），在这些条件下，手性双环钛酸酯和非手性钛酸酯不反应生成新物种。从具有不同化学计量比的成分的实验，以及在七元环钛酸酯的Ti原子上具有不同的非手性或手性OR基团的实验得出的结论是：（i）单个手性钛酸酯参与了产物形成步骤， （ii）由于空间受阻的Ti中心上配体交换的快速动力学，笨重的TADDOLate配体使Ti中心比（i-PrO）4 Ti具有更高的催化活性（表5，图3）， （iii）过量（i-

  DOI：

  10.1002/hlca.19920750704
• 作为产物：
  描述：

  甲基碘化镁 、 diethyl (4R,5R)-2-phenyl-1,3-dioxolane-4,5-dicarboxylate 生成 (4R,5R)-α,α,α',α'-tetraphenyl-2-phenyl-1,3-dioxolane-4,5-dimethanol
  参考文献：
  名称：

  Tartrate-derived aryl aldehyde acetals in the asymmetric directed metalation of chromium tricarbonyl arene complexes

  摘要：

  A series of three chromium tricarbonyl benzaldehyde acetal complexes were prepared from benzaldehyde diethyl acetal and (+)-diethyl tartrate. These compounds were ortho-lithiated by a number of bases, and the diastereoselectivity of lithiation was determined by quenching of the resulting anions with Me3SiCl. Complexes 1 and 2 were found to give moderate levels of diastereoselection, while the combination of complex 3 and 2.4 equiv of n-BuLi under equilibrating conditions gave an 86% de of silylated products. Other electrophiles gave slightly higher de's (88% to greater-than-or-equal-to 94%), and all products derived from 3 were separable by column chromatography. Hydrolysis of the ortho-methylated product to the corresponding benzaldehyde complex (-)-21 as well as X-ray structural analysis of the trimethylsilylated complex demonstrated that preferential pro-R deprotonation had occurred.

  DOI：

  10.1021/jo00075a008

文献信息

• MATTESON, DONALD S.;MICHNICK, JOHN T., ORGANOMETALLICS, 9,(1990) N2, C. 3171-3177
  作者：MATTESON, DONALD S.、MICHNICK, JOHN T.

  DOI：——

  日期：——
• On the Mechanisms of Enantioselective Reactions Using ?,?,??,?? -Tetraaryl-1,3-dioxolane-4,5-dimethanol(TADDOL)-Derived Titanates: Differences betweenC2- andC1-symmetrical TADDOLs - facts, implications and generalizations
  作者：Dieter Seebach、Dietmar A. Plattner、Albert K. Beck、Yan Ming Wang、Daniel Hunziker、Walter Petter

  DOI：10.1002/hlca.19920750704

  日期：1992.11.11

  titanate is involved in the product-forming step, (ii) that the bulky TADDOLate ligand renders the Ti-center catalytically more active than that of (i-PrO)4Ti, due to fast dynamics of ligand exchange on the sterically hindered Ti-center (Table 5, Fig. 3), and (iii) that the role of excess (i-PrO)4Ti is to remove – by ligand exchange – the product alkoxides (R*O) from the catalytically active Ti-center

  衍生自α，α，α'，α'-四芳基-1,3-二氧戊环-4,5-二甲醇（TADDOLs，由酒石酸盐制备）的钛酸酯用作二烷基锌化合物向醛的对映选择性加成的催化剂。对于为研究机理而选择的标准反应，即在苯甲醛中添加二乙基锌，TADDOLate配体上的不同芳基取代基的选择性变化很小（表2-4，示例）。0.02至0.2当量 对于手性钛酸酯，只有在过量的钛酸四异丙酯存在下才能观察到90％以上的选择性！根据NMR测量（图2），在这些条件下，手性双环钛酸酯和非手性钛酸酯不反应生成新物种。从具有不同化学计量比的成分的实验，以及在七元环钛酸酯的Ti原子上具有不同的非手性或手性OR基团的实验得出的结论是：（i）单个手性钛酸酯参与了产物形成步骤， （ii）由于空间受阻的Ti中心上配体交换的快速动力学，笨重的TADDOLate配体使Ti中心比（i-PrO）4 Ti具有更高的催化活性（表5，图3）， （iii）过量（i-
• Tartrate-derived aryl aldehyde acetals in the asymmetric directed metalation of chromium tricarbonyl arene complexes
  作者：Yoshinori Kondo、James R. Green、Jianwei Ho

  DOI：10.1021/jo00075a008

  日期：1993.11

  A series of three chromium tricarbonyl benzaldehyde acetal complexes were prepared from benzaldehyde diethyl acetal and (+)-diethyl tartrate. These compounds were ortho-lithiated by a number of bases, and the diastereoselectivity of lithiation was determined by quenching of the resulting anions with Me3SiCl. Complexes 1 and 2 were found to give moderate levels of diastereoselection, while the combination of complex 3 and 2.4 equiv of n-BuLi under equilibrating conditions gave an 86% de of silylated products. Other electrophiles gave slightly higher de's (88% to greater-than-or-equal-to 94%), and all products derived from 3 were separable by column chromatography. Hydrolysis of the ortho-methylated product to the corresponding benzaldehyde complex (-)-21 as well as X-ray structural analysis of the trimethylsilylated complex demonstrated that preferential pro-R deprotonation had occurred.