[(4R,5R)-5-[3,5-bis(phenylmethoxy)phenyl]-2,2-dimethyl-1,3-dioxolan-4-yl]methanol | 184914-51-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: [(4R,5R)-5-[3,5-bis(phenylmethoxy)phenyl]-2,2-dimethyl-1,3-dioxolan-4-yl]methanol
• CAS: 184914-51-0
• 化学式: C₂₆H₂₈O₅
• 分子量: 420.505
• InChiKey: HETPPEQKYRJKAF-JWQCQUIFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  31
• 可旋转键数：
  8
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  57.2
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  [(4R,5R)-5-[3,5-bis(phenylmethoxy)phenyl]-2,2-dimethyl-1,3-dioxolan-4-yl]methanol 在 18-冠醚-6 、 potassium carbonate 、 三乙胺 作用下， 以 二氯甲烷 、 丙酮 为溶剂， 生成
  参考文献：
  名称：

  Constitution, Configuration, and the Optical Activity of Chiral Dendrimers

  摘要：

  Three series of zeroth to second generation chiral dendrimers, 7-9, 10-12, and 13-15, were prepared by convergent methods using chiral, nonracemic AB(2) monomers 1, 2, and 3, respectively. Chiroptical data revealed a significant change in molar rotation per subunit ([Phi](D)/n) as dendrimer generation increased for dendrimers 7-9 and 10-12, but not for dendrimers 13-15, a possible indication of chiral conformational order in the former two series of dendrimers, but not in the last. However, the optical activities ([Phi](D)) of low-molecular-weight model compounds 16 (+262) and 17 (+122), prepared to simulate different regions of the dendrimer structure, suggest that as generation size increases slight constitutional changes have a strong effect on the chiroptical properties of the dendrimer subunits. Using the [Phi](D) values of these and other (18-23) low-molecular-weight model compounds, we calculated [Phi](D) values for dendrimers 7-15 that agree within 14% of the observed values. Agreement between the optical activity of the model compounds and the dendrimers leads to the conclusion that the conformational equilibria of the dendrimer subunits are not perturbed relative to those of the model compounds. Therefore, we interpreted the change in [Phi](D)/n as dendrimer generation increased for dendrimers 7-12 to be based solely on constitutional changes in the dendritic structure and not chiral conformational order.

  DOI：

  10.1021/ja970150i
• 作为产物：
  描述：

  3,5-二苄氧基苯甲醇 在 lithium aluminium tetrahydride 、 甲基磺酰胺 、 K2 、 Celite 、 sodium 、 potassium carbonate 、 对甲苯磺酸 、 氢化奎尼定 1,4-(2,3-二氮杂萘)二醚 、 pyridinium chlorochromate 、 potassium hexacyanoferrate(III) 作用下， 以 乙醚 、 乙醇 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 、 甲苯 、 叔丁醇 为溶剂， 反应 74.75h， 生成 [(4R,5R)-5-[3,5-bis(phenylmethoxy)phenyl]-2,2-dimethyl-1,3-dioxolan-4-yl]methanol
  参考文献：
  名称：

  Asymmetric Synthesis of a Series of Chiral AB₂ Monomers for Dendrimer Construction

  摘要：

  Efficient preparation of a series of four chiral, nonracemic AB(2) monomers suitable for the construction of dendrimers is presented. Monomers 1-4 possess the common structural features of a diphenolic moiety and a benzylic or aliphatic hydroxyl which render these molecules suitable for convergent dendrimer synthesis. The same basic, high-yielding, five-step sequence is employed for 1-4. Stilbene derivatives 13 and 14 are prepared by a Horner-Wadsworth-Emmons modified Wittig reaction between 3,5- or 3,4-bis(benzyloxy)benzaldehyde (8 and 10) and an ester-substituted benzylphosphonate (11 or 12). Cinnamate derivatives 21 and 22 are prepared similarly from 8 and 10 and triethyl phosphonoacetate. Chirality is introduced in the form of a 1,2-diol unit by Sharpless asymmetric dihydroxylation (AD) (>97% ee in all cases), Protection of the 1,2-diols as their acetonide derivatives provides dioxolane intermediates 17, 18, 25, and 26. Reduction of the ester groups followed by hydrogenolysis of the benzyl ethers yields AB(2) monomers 1-4 in 57-67% overall yield from 8 and 10.

  DOI：

  10.1021/jo961587w

文献信息

• Asymmetric Synthesis of a Series of Chiral AB₂ Monomers for Dendrimer Construction
  作者：James R. McElhanon、Mu-Jen Wu、Maya Escobar、Umer Chaudhry、Chun-Ling Hu、Dominic V. McGrath

  DOI：10.1021/jo961587w

  日期：1997.2.1

  Efficient preparation of a series of four chiral, nonracemic AB(2) monomers suitable for the construction of dendrimers is presented. Monomers 1-4 possess the common structural features of a diphenolic moiety and a benzylic or aliphatic hydroxyl which render these molecules suitable for convergent dendrimer synthesis. The same basic, high-yielding, five-step sequence is employed for 1-4. Stilbene derivatives 13 and 14 are prepared by a Horner-Wadsworth-Emmons modified Wittig reaction between 3,5- or 3,4-bis(benzyloxy)benzaldehyde (8 and 10) and an ester-substituted benzylphosphonate (11 or 12). Cinnamate derivatives 21 and 22 are prepared similarly from 8 and 10 and triethyl phosphonoacetate. Chirality is introduced in the form of a 1,2-diol unit by Sharpless asymmetric dihydroxylation (AD) (>97% ee in all cases), Protection of the 1,2-diols as their acetonide derivatives provides dioxolane intermediates 17, 18, 25, and 26. Reduction of the ester groups followed by hydrogenolysis of the benzyl ethers yields AB(2) monomers 1-4 in 57-67% overall yield from 8 and 10.
• Constitution, Configuration, and the Optical Activity of Chiral Dendrimers
  作者：James R. McElhanon、Dominic V. McGrath

  DOI：10.1021/ja970150i

  日期：1998.3.1

  Three series of zeroth to second generation chiral dendrimers, 7-9, 10-12, and 13-15, were prepared by convergent methods using chiral, nonracemic AB(2) monomers 1, 2, and 3, respectively. Chiroptical data revealed a significant change in molar rotation per subunit ([Phi](D)/n) as dendrimer generation increased for dendrimers 7-9 and 10-12, but not for dendrimers 13-15, a possible indication of chiral conformational order in the former two series of dendrimers, but not in the last. However, the optical activities ([Phi](D)) of low-molecular-weight model compounds 16 (+262) and 17 (+122), prepared to simulate different regions of the dendrimer structure, suggest that as generation size increases slight constitutional changes have a strong effect on the chiroptical properties of the dendrimer subunits. Using the [Phi](D) values of these and other (18-23) low-molecular-weight model compounds, we calculated [Phi](D) values for dendrimers 7-15 that agree within 14% of the observed values. Agreement between the optical activity of the model compounds and the dendrimers leads to the conclusion that the conformational equilibria of the dendrimer subunits are not perturbed relative to those of the model compounds. Therefore, we interpreted the change in [Phi](D)/n as dendrimer generation increased for dendrimers 7-12 to be based solely on constitutional changes in the dendritic structure and not chiral conformational order.