(+)-4'-tert-butyldimethylsilyloxy-2',7-(dibenzyloxy)isoflavan-3,4-diol | 1072145-55-1

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 异黄酮类化合物
• 英文名称: (+)-4'-tert-butyldimethylsilyloxy-2',7-(dibenzyloxy)isoflavan-3,4-diol
• 英文别名: (-)-4'-t-butyldimethylsilyloxy-2',7-(dibenzyloxy)-isoflavan-3,4-diol；(+)-4'-t-butyldimethylsilyloxy-2',7-(dibenzyloxy)isoflavan-3,4-diol；(3S,4R)-3-[4-[tert-butyl(dimethyl)silyl]oxy-2-phenylmethoxyphenyl]-7-phenylmethoxy-2,4-dihydrochromene-3,4-diol
• CAS: 1072145-55-1
• 化学式: C₃₅H₄₀O₆Si
• 分子量: 584.784
• InChiKey: HXMBHKZVYMMNBW-VLZNPVHKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.54
• 重原子数：
  42
• 可旋转键数：
  10
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  77.4
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (+)-4'-tert-butyldimethylsilyloxy-2',7-(dibenzyloxy)isoflavan-3,4-diol 在 palladium 10% on activated carbon 、 氢气 作用下， 以 乙醇 为溶剂， 20.0 ℃ 、241.32 kPa 条件下， 以85%的产率得到(-)-9-(t-butyldimethylsilyloxy)-glycinol
  参考文献：
  名称：

  外消旋和天然甘醇的总合成

  摘要：

  描述了外消旋和（-）-甘醇（1）的总合成。Wittig反应产生异黄酮-3-烯，从其进行无尖锐的二羟基化引入外消旋或对映体6a-羟基。12个步骤后，外消旋材料的总产率为5.5％。为掩盖敏感的间苯二酚对-官能团的保护基的一锅法设计了一种方法，并优化了条件以在随后暴露邻苯二酚二氢呋喃的邻-官能团时提示自发关闭。这些改进省去了两个步骤，并且在天然对映异构体的生产过程中将总收率提高到9.8％。

  DOI：

  10.1021/np900509f
• 作为产物：
  描述：

  2'-7-dibenzyloxy-4'-hydroxyisoflavone 在 四氧化锇 、 锂硼氢 、 AD-mix-β 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 8.0h， 生成 (+)-4'-tert-butyldimethylsilyloxy-2',7-(dibenzyloxy)isoflavan-3,4-diol
  参考文献：
  名称：

  Biomimetic Syntheses and Antiproliferative Activities of Racemic, Natural (−), and Unnnatural (+) Glyceollin I

  摘要：

  A 14-step biomimetic synthetic route to glyceollin I (1.5% overall yield) was developed and deployed to produce the natural enantiomeric form in soy, its unnatural stereoisomer, and a racemic mixture. Enantiomeric excess was assessed by asymmetric NMR shift reagents and chiral HPLC. Antiproliferative effects were measured in human breast, ovarian, and prostate cancer cell lines, with all three chiral forms exhibiting growth inhibition (GI) in the low to mid mu M range for all cells. The natural enantiomer, and in some cases the racemate, gave significantly greater GI than the unnatural stereoisomer for estrogen receptor positive (ER+) versus ER- breast/ovarian cell lines as well as for androgen receptor positive (AR(+)) versus AR(-) prostate cancer cells. Surprisingly, differences between ER+ and ER- cell lines were not altered by media estrogen conditions. These results suggest the antiproliferative mechanism of glyceollin I stereoisomers may be more complicated than strictly ER interactions.

  DOI：

  10.1021/jm101619e

文献信息

• Multigram Synthesis of Glyceollin I
  作者：Amarjit Luniwal、Rahul Khupse、Michael Reese、Jidong Liu、Mohammad El-Dakdouki、Neha Malik、Lei Fang、Paul Erhardt

  DOI：10.1021/op200112g

  日期：2011.9.16

  Scaled-up procedures and preparation of glyceollin I in multigram quantities are described. The synthesis features construction of a cis-fused ring system in high enantiomeric excess after Sharpless asymmetric dihydroxylation of a key intermediate that is initially produced by an intramolecular Wittig reaction to afford the requisite alkene while simultaneously forming the first ring. The overall yield

  描述了放大程序和制备多克数量的甘油I的方法。该合成的特征在于关键中间体的无尖锐的不对称二羟基化之后，高对映体过量的顺式稠合的环体系的构建，所述关键中间体最初由分子内Wittig反应产生，以提供所需的烯烃，同时形成第一个环。经过11个步骤，总产率为12％。
• Total Syntheses of Racemic, Natural (−) and Unnatural (+) Glyceollin I
  作者：Rahul S. Khupse、Paul W. Erhardt

  DOI：10.1021/ol802112r

  日期：2008.11.6

  The first total syntheses of racemic glyceollin I and its enantiomers are described. A Wittig approach was utilized as an entry to the appropriately substituted isoflav-3-ene so that an osmium tetroxide mediated asymmetric dihydroxylation could be deployed for stereospecific introduction of the 6a-hydroxy group. While using triphenylphosphine hydrobromide, a novel method was found for gently removing

  描述了外消旋甘油I和其对映异构体的第一批总合成。使用维蒂希（Wittig）方法作为适当取代的异黄酮3-烯的入口，以便四氧化介导的不对称二羟基化反应可用于立体定向引入6a-羟基。在使用氢溴化三苯膦时，发现了一种新方法，用于从敏感系统内存在的受保护酚羟基中轻轻去除MOM。