2',7-dibenzyloxy-4'-(tert-butyldimethylsilyloxy)isoflav-3-ene | 1072145-54-0

• 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: 2',7-dibenzyloxy-4'-(tert-butyldimethylsilyloxy)isoflav-3-ene
• 英文别名: 2',7-dibenzyloxy-4'-(t-butyldimethylsilyloxy)isoflav-3-ene；2',7-dibenzyloxy-4'-(t-butyldimethylsilyl)-isoflav-3-ene；2',7-Dibenzyloxy-4'-(t-butyldimethylsilyloxy)-isoflav-3-ene；tert-butyl-dimethyl-[3-phenylmethoxy-4-(7-phenylmethoxy-2H-chromen-3-yl)phenoxy]silane
• CAS: 1072145-54-0
• 化学式: C₃₅H₃₈O₄Si
• 分子量: 550.77
• InChiKey: KUVOEDDLPASWII-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.16
• 重原子数：
  40
• 可旋转键数：
  10
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.26
• 拓扑面积：
  36.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2',7-dibenzyloxy-4'-(tert-butyldimethylsilyloxy)isoflav-3-ene 在 四氧化锇 、 hydroquinidine 1 4-phthalazinediyl diether 、 palladium 10% on activated carbon 、 氢气 作用下， 以 乙醇 、 二氯甲烷 为溶剂， -20.0~20.0 ℃ 、241.32 kPa 条件下， 反应 4.0h， 生成 (-)-9-(t-butyldimethylsilyloxy)-glycinol
  参考文献：
  名称：

  甘油单糖醇I的多谱合成

  摘要：

  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％。

  DOI：

  10.1021/op200112g
• 作为产物：
  描述：

  2,4-二羟基苯乙酮 在 potassium tert-butylate 、 zinc diacetate 、 碘 、 三苯基膦氢溴酸盐 、 potassium carbonate 、 Selectfluor 、 乙酰氯 作用下， 以 甲醇 、 二氯甲烷 、 乙酸乙酯 、 丙酮 、 乙腈 为溶剂， 反应 42.0h， 生成 2',7-dibenzyloxy-4'-(tert-butyldimethylsilyloxy)isoflav-3-ene
  参考文献：
  名称：

  甘油单糖醇I的多谱合成

  摘要：

  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％。

  DOI：

  10.1021/op200112g

文献信息

• Total Syntheses of Racemic and Natural Glycinol
  作者：Amarjit Luniwal、Rahul S. Khupse、Michael Reese、Lei Fang、Paul W. Erhardt

  DOI：10.1021/np900509f

  日期：2009.11.30

  Total syntheses of racemic and (−)-glycinol (1) are described. A Wittig reaction produced the isoflav-3-ene from which a Sharpless dihydroxylation introduced either the racemic or enantiomeric 6a-hydroxy group. A 5.5% overall yield of racemic material was obtained after 12 steps. A method was devised for a one-pot switch of protecting groups masking a sensitive resorcinolic para-functionality, and

  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％。
• 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。
• METHODS FOR SYNTHESIZING GLYCINOLS, GLYCEOLLINS I AND II, COMPOSITIONS OF SELECTED INTERMEDIATES, AND THERAPEUTIC USES THEREOF
  申请人：Erhardt Paul W.

  公开号：US20110144195A1

  公开（公告）日：2011-06-16

  Two distinct methods are disclosed and claimed for synthesizing glyceollin I plus glyceollin II as a mixture and as their pure forms. Stereochemical isomers and various synthetic intermediates are also synthesized and claimed for their novel compositions of matter. All compounds and their mixtures are claimed for use in formulations that are useful to treat or prevent cancer, or that have utility as selective estrogen receptor modulators, such formulations including enhanced or medical foods, dietary supplements and ethical pharmaceutical agents.

  公开并声明了两种不同的方法，用于合成甘油素I和甘油素II，作为混合物和其纯形式。立体化学异构体和各种合成中间体也被合成并声明为其新颖的物质组成。所有化合物及其混合物均声明用于制剂，用于治疗或预防癌症，或具有作为选择性雌激素受体调节剂的效用，这些制剂包括增强食品、膳食补充剂和伦理药物代理。
• Methods for synthesizing glycinols, glyceollins I and II, compositions of selected intermediates, and therapeutic uses thereof
  申请人：Erhardt Paul W.

  公开号：US08563599B2

  公开（公告）日：2013-10-22

  Two distinct methods are disclosed and claimed for synthesizing glyceollin I plus glyceollin II as a mixture and as their pure forms. Stereochemical isomers and various synthetic intermediates are also synthesized and claimed for their novel compositions of matter. All compounds and their mixtures are claimed for use in formulations that are useful to treat or prevent cancer, or that have utility as selective estrogen receptor modulators, such formulations including enhanced or medical foods, dietary supplements and ethical pharmaceutical agents.

  本发明揭示了两种不同的方法，用于合成甘豆素I和甘豆素II，作为混合物和纯形式。还合成了立体化学异构体和各种合成中间体，并声明了它们的新颖物质组成。所有化合物及其混合物均声明用于制剂，可用于治疗或预防癌症，或具有作为选择性雌激素受体调节剂的效用，这些制剂包括增强型或医疗食品、膳食补充剂和道德制药剂。
• Biomimetic Syntheses and Antiproliferative Activities of Racemic, Natural (−), and Unnnatural (+) Glyceollin I
  作者：Rahul S. Khupse、Jeffrey G. Sarver、Jill A. Trendel、Nicole R. Bearss、Michael D. Reese、Thomas E. Wiese、Stephen M. Boue、Matthew E. Burow、Thomas E. Cleveland、Deepak Bhatnagar、Paul W. Erhardt

  DOI：10.1021/jm101619e

  日期：2011.5.26

  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.