1-((2S,3R)-3-Benzyloxy-2-benzyloxymethyl-butyl)-4-bromomethyl-benzene | 255827-60-2

• 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: 1-((2S,3R)-3-Benzyloxy-2-benzyloxymethyl-butyl)-4-bromomethyl-benzene
• 英文别名: 1-(bromomethyl)-4-[(2S,3R)-3-phenylmethoxy-2-(phenylmethoxymethyl)butyl]benzene
• CAS: 255827-60-2
• 化学式: C₂₆H₂₉BrO₂
• 分子量: 453.419
• InChiKey: VKYZSAKIOMSJJN-RLWLMLJZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.1
• 重原子数：
  29
• 可旋转键数：
  11
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (4R,5R)-2,2-Dimethyl-α,α,α',α'-tetra(4-hydroxyphenyl)-1,3-dioxolane-4,5-dimethanol 、 1-((2S,3R)-3-Benzyloxy-2-benzyloxymethyl-butyl)-4-bromomethyl-benzene 在 potassium carbonate 作用下， 以 丙酮 为溶剂， 反应 12.0h， 以41%的产率得到[(4R,5R)-5-[hydroxy-bis[4-[[4-[(2S,3R)-3-phenylmethoxy-2-(phenylmethoxymethyl)butyl]phenyl]methoxy]phenyl]methyl]-2,2-dimethyl-1,3-dioxolan-4-yl]-bis[4-[[4-[(2S,3R)-3-phenylmethoxy-2-(phenylmethoxymethyl)butyl]phenyl]methoxy]phenyl]methanol
  参考文献：
  名称：

  Dendritic TADDOLs: Synthesis, Characterization and Use in the Catalytic Enantioselective Addition of Et2Zn to Benzaldehyde

  摘要：

  The versatile chiral ligand for polar metal centers, TADDOL ((R,R)alpha,alpha,alpha',alpha'-tetraaryl-1,3-dioxolane-4,5-di-methanol), has been incorporated as core building block into dendrimers by way of benzylation of a fourfold phenolic derivative (hexol 2) with Frechet-type branches of up to fourth generation. These carry either benzyl (3-7) or octyl groups (33 -35) at the periphery, or they contain chiral branching units (18 - 20, 36), derived from (R)- or (S)-3-hydroxybutanoic acid. The dendritic compounds of molecular weight up to 13626 have been fully characterized, including by MALDI-TOF mass spectrometry, NMR spectroscopy, and optical activity measurements; one of the branch precursors with four octyl groups crystallized in an intriguing packing pattern. From the spectra and from the specific and molar optical rotations, there was no indication for the formation of chiral secondary structures of up to the third generation. The new TADDOLs were converted to Ti TADDOLates, which were employed as catalysts for the addition of Et2Zn to PhCHO. The stereoselectivities and the reaction rates observed with the novel catalysts were compared with those of the simple Ti TADDOLate: up to the second generation there was no detectable decrease of selectivity (= 98:2), and the rates hardly decreased up to the third generation; also, enantiomeric branches caused no change of stereoselectivity within experimental error. Thus, there may be applications for the special properties (such as high molecular weight, good solubility, spacing of central site from cross-linked polymer matrix) of dendritically modified chiral catalyst ligands.

  DOI：

  10.1002/(sici)1521-3765(19991105)5:11<3221::aid-chem3221>3.0.co;2-p
• 作为产物：
  描述：

  (2S,3R)-2-[[4-[[tert-butyl(diphenyl)silyl]oxymethyl]phenyl]methyl]butane-1,3-diol 在 四溴化碳 、 四丁基氟化铵 、 sodium hydride 、 三苯基膦 作用下， 以 四氢呋喃 为溶剂， 反应 57.25h， 生成 1-((2S,3R)-3-Benzyloxy-2-benzyloxymethyl-butyl)-4-bromomethyl-benzene
  参考文献：
  名称：

  Dendritic TADDOLs: Synthesis, Characterization and Use in the Catalytic Enantioselective Addition of Et2Zn to Benzaldehyde

  摘要：

  The versatile chiral ligand for polar metal centers, TADDOL ((R,R)alpha,alpha,alpha',alpha'-tetraaryl-1,3-dioxolane-4,5-di-methanol), has been incorporated as core building block into dendrimers by way of benzylation of a fourfold phenolic derivative (hexol 2) with Frechet-type branches of up to fourth generation. These carry either benzyl (3-7) or octyl groups (33 -35) at the periphery, or they contain chiral branching units (18 - 20, 36), derived from (R)- or (S)-3-hydroxybutanoic acid. The dendritic compounds of molecular weight up to 13626 have been fully characterized, including by MALDI-TOF mass spectrometry, NMR spectroscopy, and optical activity measurements; one of the branch precursors with four octyl groups crystallized in an intriguing packing pattern. From the spectra and from the specific and molar optical rotations, there was no indication for the formation of chiral secondary structures of up to the third generation. The new TADDOLs were converted to Ti TADDOLates, which were employed as catalysts for the addition of Et2Zn to PhCHO. The stereoselectivities and the reaction rates observed with the novel catalysts were compared with those of the simple Ti TADDOLate: up to the second generation there was no detectable decrease of selectivity (= 98:2), and the rates hardly decreased up to the third generation; also, enantiomeric branches caused no change of stereoselectivity within experimental error. Thus, there may be applications for the special properties (such as high molecular weight, good solubility, spacing of central site from cross-linked polymer matrix) of dendritically modified chiral catalyst ligands.

  DOI：

  10.1002/(sici)1521-3765(19991105)5:11<3221::aid-chem3221>3.0.co;2-p

文献信息

• Dendritic TADDOLs: Synthesis, Characterization and Use in the Catalytic Enantioselective Addition of Et2Zn to Benzaldehyde
  作者：P. Beat Rheiner、Dieter Seebach

  DOI：10.1002/(sici)1521-3765(19991105)5:11<3221::aid-chem3221>3.0.co;2-p

  日期：1999.11.5

  The versatile chiral ligand for polar metal centers, TADDOL ((R,R)alpha,alpha,alpha',alpha'-tetraaryl-1,3-dioxolane-4,5-di-methanol), has been incorporated as core building block into dendrimers by way of benzylation of a fourfold phenolic derivative (hexol 2) with Frechet-type branches of up to fourth generation. These carry either benzyl (3-7) or octyl groups (33 -35) at the periphery, or they contain chiral branching units (18 - 20, 36), derived from (R)- or (S)-3-hydroxybutanoic acid. The dendritic compounds of molecular weight up to 13626 have been fully characterized, including by MALDI-TOF mass spectrometry, NMR spectroscopy, and optical activity measurements; one of the branch precursors with four octyl groups crystallized in an intriguing packing pattern. From the spectra and from the specific and molar optical rotations, there was no indication for the formation of chiral secondary structures of up to the third generation. The new TADDOLs were converted to Ti TADDOLates, which were employed as catalysts for the addition of Et2Zn to PhCHO. The stereoselectivities and the reaction rates observed with the novel catalysts were compared with those of the simple Ti TADDOLate: up to the second generation there was no detectable decrease of selectivity (= 98:2), and the rates hardly decreased up to the third generation; also, enantiomeric branches caused no change of stereoselectivity within experimental error. Thus, there may be applications for the special properties (such as high molecular weight, good solubility, spacing of central site from cross-linked polymer matrix) of dendritically modified chiral catalyst ligands.