2,4,6-trihydroxyacetophenone-3,5-di-C-glucoside | 160913-21-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2,4,6-trihydroxyacetophenone-3,5-di-C-glucoside
• 英文别名: di-C-β-D-glucopyranosylphloroacetophenone；3,5-di-C-β-D-glucopyranosylphloroacetophenone；3',5'-di-C-β-D-glucosyl-2',4',6'-trihydroxyacetophenone；1-[2,4,6-trihydroxy-3,5-bis[(2S,3R,4R,5S,6R)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]phenyl]ethanone
• CAS: 160913-21-3
• 化学式: C₂₀H₂₈O₁₄
• 分子量: 492.434
• InChiKey: DFBBFWZHBXXZGI-YBFIPBEFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -3.8
• 重原子数：
  34
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.65
• 拓扑面积：
  258
• 氢给体数：
  11
• 氢受体数：
  14

反应信息

• 作为反应物：
  描述：

  2,4,6-trihydroxyacetophenone-3,5-di-C-glucoside 在 盐酸 、 氢氧化钾 、 potassium carbonate 作用下， 以 甲醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 25.25h， 生成 6,8-di-C-β-D-glucopyranosylnaringenin
  参考文献：
  名称：

  Total synthesis of three naturally occurring 6,8-di-C-glycosylflavonoids: phloretin, naringenin, and apigenin bis-C-β-d-glucosides

  摘要：

  Three naturally occurring di-C-glycosylflavonoids, phloretin (dihydrochalcone), naringenin (flavanone), and apigenin (flavone) bis-6,8-C-beta-D-glucopyranosides (4, 5, and 6), were synthesized in total yields of 52.3%, 53.5%, and 36.4%, respectively, starting from the key compound, di-C-beta-D-glucopyranosylphloroacetophenone (1). Benzyl protection of the phenolic hydroxyls in I and a subsequent aldol condensation with benzyloxybenzaldehyde led to the production of chalcone 3, which, after hydrogenolysis or acid hydrolysis and deprotection, gave 4 and 5, respectively. The acetylation of 5, followed by DDQ oxidation and deprotection, gave 6. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.carres.2006.02.019
• 作为产物：
  描述：

  尿苷(5')二氢二磷酰(1)-alpha-D-葡萄糖 、 2,4,6-三羟基苯乙酮一水合物 在 recombinant di‑C‑glycosyltransferase from Glycyrrhiza glabra 作用下， 以 氘代二甲亚砜 、 aq. phosphate buffer 为溶剂， 反应 2.0h， 以1.3 mg的产率得到2,4,6-trihydroxyacetophenone-3,5-di-C-glucoside
  参考文献：
  名称：

  光果甘草高效二-C-糖基转移酶的功能表征和结构基础

  摘要：

  从药用植物光果甘草中发现了一种高效的二-C-糖基转移酶GgCGT。GgCGT 催化含氟丙酮底物的两步二 C-糖基化，转化率 >98%。为了阐明 GgCGT 的催化机制，我们分别解析了其与 UDP-Glc、UDP-Gal、UDP/根皮素和 UDP/nothofagin 复合物的晶体结构。结构分析表明，糖供体选择性受糖羟基与 D390 和其他关键残基的氢键相互作用控制。GgCGT 的二 C 糖基化能力归因于宽敞的底物结合隧道，G389K 突变可以将二 C 糖基化转换为单 C 糖基化。GgCGT 是第一个具有晶体结构的双 C-糖基转移酶，以及第一个含有糖受体的复杂结构的C-糖基转移酶。这项工作有利于开发有效的生物催化剂，以合成具有药用潜力的 C-糖苷。

  DOI：

  10.1021/jacs.9b12211

文献信息

• Total Synthesis of Two Isoflavone Bis-C-glycosides: Genistein and Orobol 6,8-Di-C-β-d-glucopyranosides
  作者：Shingo Sato、Hidetoshi Ishikawa

  DOI：10.1055/s-0030-1257859

  日期：2010.9

  This paper describes the first successful synthesis of two isoflavone bis-C-glycosides, genistein and orobol 6,8-di-C-β-d-glucopyranosides from phloroacetophenone bis-C-glycoside in total yields of 27 and 19%, respectively, using a four-step reaction: direct C-glycosylation of phloroacetophenone with unprotected d-glucose; chalcone synthesis by aldol condensation; acetal synthesis by oxidative rearrangement using DIB and p-TsOH; and formation of the isoflavone ring using HCl, without protection of the glucose moiety.

  本文描述了首次成功合成两种异黄酮双C-糖苷，分别为大豆苷和黄酮苷6,8-二C-β-d-葡萄糖苷，来源于氟代酮双C-糖苷，整体产率分别为27%和19%。该合成过程采用了四步反应：首先是未保护的D-葡萄糖与氟代酮的直接C-糖苷化；然后通过醛缩合合成查尔酮；接着通过氧化重排使用DIB和对甲苯磺酸合成醚；最后在不保护葡萄糖结构的情况下，使用HCl形成异黄酮环。
• Cleavage of the C–C linkage between the sugar and the aglycon in C-glycosylphloroacetophenone, and the NMR spectral characteristics of the resulting di-C-glycosyl compound
  作者：Toshihiro Kumazawa、Takayuki Kimura、Shigeru Matsuba、Shingo Sato、Jun-ichi Onodera

  DOI：10.1016/s0008-6215(01)00183-5

  日期：2001.8

  with a cation-exchange resin in anhydrous acetonitrile afforded both a phloroacetophenone and a di-C-beta-D-glucopyranosylphloroacetophenone. Treatment of an unprotected mono-C-(2-deoxy-beta-D-arabino-hexopyranosyl)phloroacetophenone (mono-C-2-deoxy-beta-D-glucopyranosylphloroacetophenone) also afforded both the aglycon and di-C-(2-deoxy-beta-D-arabino-hexopyranosyl)phloroacetophenone. The reaction mixtures

  用无水乙腈中的阳离子交换树脂处理未保护的单-C-β-D-吡喃葡萄糖基苯乙酮，同时得到苯乙酰苯乙酮和二-C-β-D-吡喃葡萄糖基苯乙酮。对未保护的单-C-（2-脱氧-β-D-阿拉伯糖基-己吡喃糖基）苯乙酮（单-C-2-脱氧-β-D-吡喃葡糖基苯乙酮）的处理也提供了糖苷配基和二-C-（2-脱氧-β-D-阿拉伯糖-己吡喃糖基）苯乙酮。将反应混合物乙酰化，并通过NMR光谱确定分离的产物的结构。这是在芳基C-糖基衍生物中糖和糖苷配基之间的CC键化学裂解过程中形成二-C-糖基化合物的第一个证明。
• Synthesis and antihyperglycemic activity of phenolic C-glycosides
  作者：Preeti Rawat、Manmeet Kumar、Neha Rahuja、Daya Shankar Lal Srivastava、Arvind Kumar Srivastava、Rakesh Maurya

  DOI：10.1016/j.bmcl.2010.11.031

  日期：2011.1

  Various phenolic C-glycosides were evaluated for their in vitro and in vivo antihyperglycemic activity employing glucose uptake by rat muscle cell lines (L-6) and low dosed-streptozotocin-induced diabetic rats, respectively. Some of phenolic C-glycosides were isolated from Pterocarpus marsupium and Ulmus wallichiana and other were synthesized by unprotected sugar and phloroacetophenone using Sc(OTf)(3) in aqueous ethanol. Eight among tested compounds showed significant lowering of blood glucose level on low dosed-streptozotocin-induced diabetic rats. The compound 24 lowered the blood glucose levels by 34.9% and 33.6% during 0-5 h and 0-24 h, respectively, at the dose of 25 mg/kg body weight which is comparable to standard antidiabetic drug metformin. (C) 2010 Elsevier Ltd. All rights reserved.
• Environmentally friendly C-glycosylation of phloroacetophenone with unprotected d-glucose using scandium(III) trifluoromethanesulfonate in aqueous media: key compounds for the syntheses of mono- and di-C-glucosylflavonoids
  作者：Shingo Sato、Toshiki Akiya、Toshiyuki Suzuki、Jun-ichi Onodera

  DOI：10.1016/j.carres.2004.07.023

  日期：2004.10

  The direct C-glycosylation of phloroacetophenone with an unprotected D-glucose in aqueous media using scandium(III) trifluoromethanesulfonate (Sc(OTf)(3)) as the catalyst, gave mono- and bis-C-beta-glycosylic compounds in highest total yield of 81%. The second and third use of the recovered Sc(OTf)(3) afforded them in total yields of 56% and 53%, respectively. (C) 2004 Elsevier Ltd. All rights reserved.
• Functional Characterization and Structural Basis of an Efficient Di-<i>C</i>-glycosyltransferase from <i>Glycyrrhiza glabra</i>
  作者：Meng Zhang、Fu-Dong Li、Kai Li、Zi-Long Wang、Yu-Xi Wang、Jun-Bin He、Hui-Fei Su、Zhong-Yi Zhang、Chang-Biao Chi、Xiao-Meng Shi、Cai-Hong Yun、Zhi-Yong Zhang、Zhen-Ming Liu、Liang-Ren Zhang、Dong-Hui Yang、Ming Ma、Xue Qiao、Min Ye

  DOI：10.1021/jacs.9b12211

  日期：2020.2.19

  A highly efficient di-C-glycosyltransferase GgCGT was discovered from the medicinal plant Glycyrrhiza glabra. GgCGT catalyzes a two-step di-C-glycosylation of flopropione-containing substrates with conversion rates of >98%. To elucidate the catalytic mechanisms of GgCGT, we solved its crystal structures in complex with UDP-Glc, UDP-Gal, UDP/phloretin, and UDP/nothofagin, respectively. Structural analysis

  从药用植物光果甘草中发现了一种高效的二-C-糖基转移酶GgCGT。GgCGT 催化含氟丙酮底物的两步二 C-糖基化，转化率 >98%。为了阐明 GgCGT 的催化机制，我们分别解析了其与 UDP-Glc、UDP-Gal、UDP/根皮素和 UDP/nothofagin 复合物的晶体结构。结构分析表明，糖供体选择性受糖羟基与 D390 和其他关键残基的氢键相互作用控制。GgCGT 的二 C 糖基化能力归因于宽敞的底物结合隧道，G389K 突变可以将二 C 糖基化转换为单 C 糖基化。GgCGT 是第一个具有晶体结构的双 C-糖基转移酶，以及第一个含有糖受体的复杂结构的C-糖基转移酶。这项工作有利于开发有效的生物催化剂，以合成具有药用潜力的 C-糖苷。