(R,R)-4-<4'-(hydroxymethyl)phenyl>-5-<3',5'-bis(benzyloxy)phenyl>-2,2-dimethyl-1,3-dioxolane | 202578-87-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: (R,R)-4-<4'-(hydroxymethyl)phenyl>-5-<3',5'-bis(benzyloxy)phenyl>-2,2-dimethyl-1,3-dioxolane
• 英文别名: [4-[(4R,5R)-5-[3,5-bis(phenylmethoxy)phenyl]-2,2-dimethyl-1,3-dioxolan-4-yl]phenyl]methanol
• CAS: 202578-87-8
• 化学式: C₃₂H₃₂O₅
• 分子量: 496.603
• InChiKey: ILQNNWCYLIEAML-FIRIVFDPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.5
• 重原子数：
  37
• 可旋转键数：
  9
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.25
• 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：

  (R,R)-4-<4'-(hydroxymethyl)phenyl>-5-<3',5'-bis(benzyloxy)phenyl>-2,2-dimethyl-1,3-dioxolane 在 silica gel 、 4-acetylamino-2,2,6,6-tetramethylpiperidine-1-oxoammonium perchlorate 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 以100%的产率得到4-[(4R,5R)-5-(3,5-Bis-benzyloxy-phenyl)-2,2-dimethyl-[1,3]dioxolan-4-yl]-benzaldehyde
  参考文献：
  名称：

  Oxoammonium Salts. 6.¹ 4-Acetylamino-2,2,6,6-tetramethylpiperidine-1-oxoammonium Perchlorate:  A Stable and Convenient Reagent for the Oxidation of Alcohols. Silica Gel Catalysis

  摘要：

  4-Acetylamino-2,2,6,6-tetramethylpiperidine-1-oxoammonium perchlorate, 1, is a stable, nonhygroscopic oxoammonium salt that is easily prepared and can be used for the oxidation of alcohols to ketones or aldehydes in near quantitative yields. The reaction is colorimetric, does not require anhydrous conditions, does not involve heavy metals, and can be carried out conveniently. Furthermore, the oxidant can be easily regenerated. The oxidation is somewhat specific in that the relative reactivities of an allyl alcohol (geraniol), benzaldehyde, and 1-decanol are about 100: 1:0.1. The reaction is catalyzed by silica gel.

  DOI：

  10.1021/jo981322c
• 作为产物：
  描述：

  methyl 4-[(4R,5R)-5-[3,5-bis(phenylmethoxy)phenyl]-2,2-dimethyl-1,3-dioxolan-4-yl]benzoate 在 lithium aluminium tetrahydride 作用下， 以 乙醚 为溶剂， 生成 (R,R)-4-<4'-(hydroxymethyl)phenyl>-5-<3',5'-bis(benzyloxy)phenyl>-2,2-dimethyl-1,3-dioxolane
  参考文献：
  名称：

  一种从手性，非外消旋的合成单体中高度官能化的树枝状聚合物的方法

  摘要：

  提出了一种具有由手性，非外消旋的氢安息香单体单元构成的具有高功能内部结构的树枝状聚合物的方法。使用不对称二羟基化（AD）制备光学纯的单体单元，并通过会聚生长策略构建代表性的树枝状大分子。

  DOI：

  10.1016/0040-4039(96)01295-6

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.
• Synthesis and Chiroptical Analysis of Optically Active Chiral Shell Dendrons
  作者：Denise M. Junge、Mu-Jen Wu、James R. McElhanon、Dominic V. McGrath

  DOI：10.1021/jo000529e

  日期：2000.8.1

  We have prepared a series of chiral dendrons (1-4) in which chiral subunits are placed in individual generational shells at varying distances from the focal point. The optical activity of these chiral dendritic structures is successfully modeled using structurally similar low-molecular weight model compounds. In dendrons 1a and 1b a chiral subunit is directly adjacent to the focal point, whereas in dendrons 2, 3, and 4a,b the chiral subunits are incorporated in the interior of the dendron. A marked difference in optical activity between the former (1a and 1b) and latter (2, 3, 4a,b) dendrons is mirrored in the optical activities of model compounds 12a, 12b, 19a, and 19b. These model compounds directly mimic the surrounding constitution of the chiral subunits in the dendrons. This successful analysis of the chiroptical data using low-molecular weight model compounds suggests that these dendrons do not possess conformational order in solution.
• 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.