3,6,9-三羟基紫檀素 | 69393-95-9

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 异黄酮类化合物
• 中文名称: 3,6,9-三羟基紫檀素
• 英文名称: glycinol
• 英文别名: (-)-Glycinol；(6aS,11aS)-6,11a-dihydro-[1]benzofuro[3,2-c]chromene-3,6a,9-triol
• CAS: 69393-95-9
• 化学式: C₁₅H₁₂O₅
• 分子量: 272.257
• InChiKey: QMXOFBXZEKTJIK-LSDHHAIUSA-N

物化性质

• 熔点：
  108-112 °C
• 沸点：
  527.0±50.0 °C(Predicted)
• 密度：
  1.592±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  20
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  79.2
• 氢给体数：
  3
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  3,6,9-三羟基紫檀素 、 DMAPP 生成 4-Dimethylallylglycinol 、 pyrophosphoric acid
  参考文献：
  名称：

  翼果 4-二甲基烯丙基转移酶 cDNA 的分子克隆和表征，催化甘油甘油蛋白（一种大豆植物抗毒素）生物合成中的关键异戊二烯化步骤。

  摘要：

  Glyceollins 是大豆 (Glycine max) 植物抗毒素，具有源自 C5 异戊二烯基部分的环醚装饰的蝶果类骨架。在现代植物生物化学的早期阶段，参与甘油生物合成的酶已被彻底表征，并且已经克隆了许多编码异黄酮生物合成酶的基因，但一些用于后期生物合成步骤的基因仍未鉴定。特别是负责将二甲基烯丙基链添加到紫檀木的异戊二烯基转移酶由于多酚核心和类异戊二烯部分的关键偶联过程而引起了许多研究人员的大量关注。本研究将候选基因范围缩小到三个大豆表达的序列标签序列，这些序列与编码生育酚生物合成途径的 homogentisate phytyltransferase 的基因同源，并在其中鉴定了编码二甲基烯丙基二磷酸的 cDNA：(6aS, 11aS)-3,9,6a-trihydroxypterocarpan [( -)-glycinol] 4-二甲基烯丙基转移酶 (G4DT) 产生甘油 I 的直接前体。

  DOI：

  10.1104/pp.108.123679
• 作为产物：
  描述：

  (+)-variabilin 在 二苯基膦酸锂 作用下， 以 二丁醚 为溶剂， 以29%的产率得到3,6,9-三羟基紫檀素
  参考文献：
  名称：

  Asymmetric Total Syntheses of (−)-Variabilin and (−)-Glycinol

  摘要：

  Total syntheses of (-)-variabilin and (-)-glycinol have been accomplished, using the catalytic, asymmetric "Interrupted" Feist-Benary reaction (IFB) as the key transformation to introduce both stereogenic centers. A monoquinidine pyrimidinyl ether catalyst affords the IFB products In over 90% ee in both cases. Other key steps include an intramolecular Buohwald-Hartwig coupling and a nickel-catalyzed aryl tosylate reduction.

  DOI：

  10.1021/ol201332u

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％。
• Methods for Synthesizing Glycinols, Glyceollins I and II and Isoflavenes and Chromanes Using A Wittig Reaction, and Compositions Made Therewith
  申请人：Erhardt Paul W.

  公开号：US20120115942A1

  公开（公告）日：2012-05-10

  Methods for synthesizing glycinols, glyceollins I and II, and isoflavene and chromane compounds using a Wittig reaction, compositions made therewith, and uses thereof are described.

  本文描述了使用Wittig反应合成甘氨醇、甘豆素I和II、异黄酮和色酮化合物的方法，制备的组合物以及它们的用途。
• Anti-osteoporotic and antioxidant activities of chemical constituents of the aerial parts of Ducrosia ismaelis
  作者：Abubaker M.A. Morgan、Hyun Woo Lee、Sang-Hyun Lee、Chi-Hwan Lim、Hae-Dong Jang、Young Ho Kim

  DOI：10.1016/j.bmcl.2014.05.077

  日期：2014.8

  A new pterocarpan glycoside, glycino1-3-O-beta-D-glucopyranoside (1), and a new dihydrochalcone glycoside, ismaeloside A (2), were isolated together with 13 known compounds, including several flavonoids (3-8), lignans (9-11), and phenolic compounds (12-15), from the methanol extract of the aerial parts of Ducrosia ismaelis. The chemical structures of these compounds were elucidated from spectroscopic data and by comparison of these data with previously published results. The anti-osteoporotic and antioxidant activities of the isolated compounds were assessed using tartrate-resistant acid phosphatase (TRAP), oxygen radical absorbance capacity (ORAC), and reducing capacity assays. Compound 15 exhibited a dose-dependent inhibition of osteoclastic TRAP activity with a TRAP value of 86.05 +/- 6.55% of the control at a concentration of 10 mu M. Compounds 1,3-5, and 8 showed potent peroxyl radical-scavenging capacities with ORAC values of 22.79 +/- 0.90, 25.57 +/- 0.49, 20.41 +/- 0.63, 26.55 +/- 0.42, and 24.83 +/- 0.12 mu M Trolox equivalents (TE) at 10 mu M, respectively. Only compound 9 was able to significantly reduce Cu(I) with 23.44 mu M TE at a concentration of 10 mu M. All of the aforementioned compounds were isolated for the first time from a Ducrosia species. (C) 2014 Elsevier Ltd. All rights reserved.
• Induction of phytoalexin synthesis in soybean. Stereospecific 3,9-dihydroxypterocarpan 6a-hydroxylase from elicitor-induced soybean cell cultures
  作者：Marie-Luise HAGMANN、Werner HELLER、Hans GRISEBACH

  DOI：10.1111/j.1432-1033.1984.tb08259.x

  日期：1984.7

  A microsomal preparation from elicitor‐challenged soybean cell suspension cultures catalyzes an NADPH‐dependent and dioxygen‐dependent 6a‐hydroxylation of 3,9‐dihydroxypterocarpan to 3,6a,9‐trihydroxypterocarpan. The latter is a precursor for the soybean phytoalexin glyceollin. No reaction is observed with NADH. The 6a‐hydroxylase is inhibited by cytochrome c.Optical rotatory dispersion spectra of the enzymatic product formed from racemic dihydroxypterocarpan and of the remaining unreacted substrate proved that the product has the natural (6aS, 11aS)‐configuration and that hydroxylation proceeds with retention of configuration.The 6a‐hydroxylase was also found in elicitor‐challenged soybean seedlings. The results indicate that the 6a‐hydroxylase is specifically involved in the biosynthesis of glyceollin.
• US8507549B2
  申请人：——

  公开号：US8507549B2

  公开（公告）日：2013-08-13