(R)-1-((2S,4R,6S)-6-(2-((4-methoxybenzyl)oxy)ethyl)-2-phenyl-1,3-dioxan-4-yl)pent-4-en-2-ol | 1443040-54-7

• 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: (R)-1-((2S,4R,6S)-6-(2-((4-methoxybenzyl)oxy)ethyl)-2-phenyl-1,3-dioxan-4-yl)pent-4-en-2-ol
• 英文别名: (2R)-1-[(2S,4R,6S)-6-[2-[(4-methoxyphenyl)methoxy]ethyl]-2-phenyl-1,3-dioxan-4-yl]pent-4-en-2-ol
• CAS: 1443040-54-7
• 化学式: C₂₅H₃₂O₅
• 分子量: 412.526
• InChiKey: YNHZHUAOLLLQAX-WUEDSLEZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  30
• 可旋转键数：
  11
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.44
• 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)-1-((2S,4R,6S)-6-(2-((4-methoxybenzyl)oxy)ethyl)-2-phenyl-1,3-dioxan-4-yl)pent-4-en-2-ol 在 RuCl2(1,3-dimesityl-imidazolidin-2-yl)(PCy3)(=CHPh) 、 potassium tert-butylate 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 3.75h， 生成 ethyl 2-((2S,4S,6S)-6-(((2S,4S,6S)-6-(2-((4-methoxybenzyl)oxy)ethyl)-2-phenyl-1,3-dioxan-4-yl)methyl)-2-phenyl-1,3-dioxan-4-yl)acetate
  参考文献：
  名称：

  隐烯醇A和B的多烯策略的不对称迭代水合

  摘要：

  摘要 两种迭代不对称水合的发展接近所有的合成顺式-和顺式/反/顺式-1,3,5,7四醇基序进行说明。这些伪对称产物是1，3-己醇产物的合成前体。证明了该路线对所有syn -1,3,5,7-四醇非对映异构体的实用性，并证明其可用于合成隐甲酚A和B，以及立体异构体。 两种迭代不对称水合的发展接近所有的合成顺式-和顺式/反/顺式-1,3,5,7四醇基序进行说明。这些伪对称产物是1，3-己醇产物的合成前体。证明了该路线对所有syn -1,3,5,7-四醇非对映异构体的实用性，并证明其可用于合成隐甲酚A和B，以及立体异构体。

  DOI：

  10.1055/s-0035-1561607
• 作为产物：
  描述：

  (R,E)-methyl 5-hydroxy-7-((4-methoxybenzyl)oxy)hept-2-enoate 在 potassium tert-butylate 、 二异丁基氢化铝 、 scandium tris(trifluoromethanesulfonate) 、 (3aS,7aS)-1,3-bis[(4-bromophenyl)methyl]-2-chlorooctahydro-2-(2-propenyl)-1H-1,3,2-benzodiazasilole 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 为溶剂， 反应 12.0h， 生成 (R)-1-((2S,4R,6S)-6-(2-((4-methoxybenzyl)oxy)ethyl)-2-phenyl-1,3-dioxan-4-yl)pent-4-en-2-ol
  参考文献：
  名称：

  Cryptocaryols A and B: Total Syntheses, Stereochemical Revision, Structure Elucidation, and Structure–Activity Relationship

  摘要：

  The first total syntheses and structural elucidation of cryptocaryol A and ayptocaryol B were achieved in 23 and 25 linear steps, respectively. The synthesis relied on the use Of a key pseudo-C, symmetric pentaol intermediate, which in a stereochemically divergent manner was converted into either enantiomer as well as diastereomers. This synthetic effort enabled the first structure-activity relationships of this class of PDCD4 stabilizing natural products.

  DOI：

  10.1021/ja404401f

文献信息

• Cryptocaryol Structure–Activity Relationship Study of Cancer Cell Cytotoxicity and Ability to Stabilize PDCD4
  作者：Michael F. Cuccarese、Yanping Wang、Penny J. Beuning、George A. O’Doherty

  DOI：10.1021/ml4005039

  日期：2014.5.8

  The synthetic cryptocaryols A and B and a series of their analogues have been evaluated for their cytotoxicity and their ability to stabilize the tumor suppressor PDCD4. Cytotoxicities in the 3 to 30 mu M range were found. Both the cytotoxicity and PDCD4 stabilizing ability were tolerant of large stereochemical changes to the molecule. Co-dosing studies with cryptocaryols A and B and several known cancer drugs showed no measuable enhancement in cancer drug cytotoxicity.
• Hydrogen-Bond Networks: Strengths of Different Types of Hydrogen Bonds and An Alternative to the Low Barrier Hydrogen-Bond Proposal
  作者：Alireza Shokri、Yanping Wang、George A. O’Doherty、Xue-Bin Wang、Steven R. Kass

  DOI：10.1021/ja408762r

  日期：2013.11.27

  We report quantifying the strengths of different types of hydrogen bonds in hydrogen-bond networks (HBNs) via measurement of the adiabatic electron detachment energy of the conjugate base of a small covalent polyol model compound (i.e., (HOCH2CH2CH(OH)CH2)(2)CHOH) in the gas phase and the pK(a) of the corresponding acid in DMSO. The latter result reveals that the hydrogen bonds to the charged center and those that are one solvation shell further away (i.e., primary and secondary) provide 5.3 and 2.5 pK(a) units of stabilization per hydrogen bond in DMSO. Computations indicate that these energies increase to 8.4 and 3.9 pK(a) units in benzene and that the total stabilizations are 16 (DMSO) and 25 (benzene) pK(a) units. Calculations on a larger linear heptaol (i.e., (HOCH2CH2CH(OH)CH2CH(OH)CH2)(2)CHOH) reveal that the terminal hydroxyl groups each contribute 0.6 pK(a) units of stabilization in DMSO and 1.1 pK(a) units in benzene. All of these results taken together indicate that the presence of a charged center can provide a powerful energetic driving force for enzyme catalysis and conformational changes such as in protein folding due to multiple hydrogen bonds in a HBN.
• Asymmetric Iterative Hydration of Polyene Strategy to Cryptocaryols A and B
  作者：George O’Doherty、Thomas Hunter、Yanping Wang、Jiamin Zheng

  DOI：10.1055/s-0035-1561607

  日期：——

  development of two iterative asymmetric hydration approaches to the synthesis of all syn- and syn/anti/syn-1,3,5,7-tetraol motifs is described. These pseudo-symmetric products are synthetic precursors for 1,3-hexol products. The utility of the route to the all syn-1,3,5,7-tetraol diastereoisomer was demonstrated with its use in the synthesis of cryptocaryols A and B, as well as, stereoisomers. The development

  摘要 两种迭代不对称水合的发展接近所有的合成顺式-和顺式/反/顺式-1,3,5,7四醇基序进行说明。这些伪对称产物是1，3-己醇产物的合成前体。证明了该路线对所有syn -1,3,5,7-四醇非对映异构体的实用性，并证明其可用于合成隐甲酚A和B，以及立体异构体。 两种迭代不对称水合的发展接近所有的合成顺式-和顺式/反/顺式-1,3,5,7四醇基序进行说明。这些伪对称产物是1，3-己醇产物的合成前体。证明了该路线对所有syn -1,3,5,7-四醇非对映异构体的实用性，并证明其可用于合成隐甲酚A和B，以及立体异构体。
• Cryptocaryols A and B: Total Syntheses, Stereochemical Revision, Structure Elucidation, and Structure–Activity Relationship
  作者：Yanping Wang、George A. O’Doherty

  DOI：10.1021/ja404401f

  日期：2013.6.26

  The first total syntheses and structural elucidation of cryptocaryol A and ayptocaryol B were achieved in 23 and 25 linear steps, respectively. The synthesis relied on the use Of a key pseudo-C, symmetric pentaol intermediate, which in a stereochemically divergent manner was converted into either enantiomer as well as diastereomers. This synthetic effort enabled the first structure-activity relationships of this class of PDCD4 stabilizing natural products.