4-hydroxy-3-methoxybenzyl-β-D-glucopyranoside

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4-hydroxy-3-methoxybenzyl-β-D-glucopyranoside
• 英文别名: 4-hydroxy-3-methoxy benzyl-β-D-glucoside；vanillyl alcohol-7-O-β-D-glucopyranoside；vanillyl 4-O-β-D-glucopyranoside；Vanillyl beta-D-glucopyranoside；(2R,3R,4S,5S,6R)-2-[(4-hydroxy-3-methoxyphenyl)methoxy]-6-(hydroxymethyl)oxane-3,4,5-triol
• 化学式: C₁₄H₂₀O₈
• 分子量: 316.308
• InChiKey: XNUBWLDOGBNCKT-RKQHYHRCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -1.1
• 重原子数：
  22
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  129
• 氢给体数：
  5
• 氢受体数：
  8

反应信息

• 作为产物：
  描述：

  乙酰香兰素 在 sodium tetrahydroborate 、 磷酸 、 碘 、 sodium methylate 、 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 甲醇 、 乙腈 为溶剂， 反应 0.67h， 生成 4-hydroxy-3-methoxybenzyl-β-D-glucopyranoside
  参考文献：
  名称：

  A selective and mild glycosylation method of natural phenolic alcohols

  摘要：

  几种生物活性的天然p-羟基苯丙基β-D-葡萄糖苷，如香草基β-D-葡萄糖苷、沙利度苷和异云杉醇苷，以及它们的糖苷类似物，通过简单的反应序列制备。通过利用乙酰化的葡萄糖溴化物以及芳香基团和温和的糖苷化促进剂，实现了高效的合成方法。去糖基物质p-O-乙酰化芳基丙基醇是通过还原相应的乙酰化醛或酸制备的。研究了各种立体选择性的1,2-trans-O-糖基化方法，包括DDQ-碘或ZnO-ZnCl2催化剂组合。其中，ZnO-碘已被确认为一种新的糖苷化促进剂，并成功应用于立体选择性糖苷合成。最终产品通过传统的Zemplén去乙酰化获得。

  DOI：

  10.3762/bjoc.12.51

文献信息

• Biotransformation of Benzaldehyde-Type and Acetophenone-Type Derivatives by Pharbitis nil Hairy Roots
  作者：Hideki Kanho、Sayaka Yaoya、Nobuo Kawahara、Takahisa Nakane、Yoichi Takase、Kazuo Masuda、Masanori Kuroyanagi

  DOI：10.1248/cpb.53.361

  日期：——

  The glucosylation of some coumarin and flavone derivatives on incubation with the hairy roots of morning glory (Pharbitis nil) was previously reported. We further studied the biotransformation of benzaldehyde- and acetophenone-type derivatives. Vanillin and isovanillin were reduced to alcoholic derivatives and glucosylated at the phenolic and the alcoholic hydroxyl groups. In the case of 3,4-dihydroxybenzaldehyde, the formyl group was reduced and the 3-hydroxyl or 4-hydroxyl groups were glucosylated to give monoglucosides. The 3-hydroxyl group was predominantly glucosylated to the 4-hydroxyl group. 4-β-D-Glucopyranosyloxy-3-methoxybenzylalcohol was obtained in low yield. In time-course experiments with vanillin, it was found that the high-level reduction of the formyl group and glucosylation of the phenolic hydroxyl group occurred, and finally 4-O-β-D-glucopyranosylvanillylalcohol was obtained as the main product. In the case of 3,4-dimethoxybenzaldehyde, 3,4,5-trimethoxybenzaldehyde, and salicylaldehyde, the formyl groups were reduced, and then the hydroxyl groups at the benyl position were glucosylated to give alcoholic glucosides in relatively high yields. In 4-hydroxy-3-methoxyacetophenone, the 4-hydroxyl group was glucosylated and two dimerized glucosides, biphenyl and biphenylether types, were obtained in low yields. In acetophenone, 1-β-D-glucopyranosyloxy-1-phenylethane and 2-β-D-glucopyranosyloxyacetophenone were obtained. As mentioned above P. nil hairy roots showed various biotransformative activities including glucosylation of phenolic and benzylic hydroxyl groups, reduction of the formyl group near the benzene ring, and phenol oxidation dimerization. The glucosylation reaction was especially interesting for the production of valuable glucosides.

  之前已有研究报告显示，某些香豆素和黄酮衍生物在与牵牛花毛根（Pharbitis nil）孵育时发生了葡萄糖化反应。我们进一步研究了苯甲醛和乙酰苯酮类衍生物的生物转化。香草醛和异香草醛被还原为醇类衍生物，并分别在酚羟基和醇羟基上发生了葡萄糖化。在3,4-二羟基苯甲醛的情况下，甲醛基被还原，而3-羟基或4-羟基则被葡萄糖化，从而生成单糖苷。3-羟基主要葡萄糖化为4-羟基。4-β-D-葡萄糖吡喃酯氧基-3-甲氧基苄醇的产率较低。在与香草醛的时间过程实验中，发现甲醛基的高水平还原和酚羟基的葡萄糖化同时发生，最终获得了4-O-β-D-葡萄糖吡喃醇香草醇作为主要产物。在3,4-二甲氧基苯甲醛、3,4,5-三甲氧基苯甲醛和水杨醛的情况下，甲醛基被还原后，苄位的羟基被葡萄糖化，生成的醇类葡萄糖苷的产率相对较高。在4-羟基-3-甲氧基乙酰苯酮中，4-羟基被葡萄糖化，并生成了两种二聚葡萄糖苷，即联苯和联苯醚类，产率较低。在乙酰苯酮中，得到1-β-D-葡萄糖吡喃酯氧基-1-苯乙烯和2-β-D-葡萄糖吡喃酯氧基乙酰苯酮。如上所述，P. nil毛根显示了多种生物转化活性，包括酚羟基和苄羟基的葡萄糖化、苯环附近甲醛基的还原以及酚氧化二聚化。葡萄糖化反应尤其值得关注，因为它能够产生有价值的葡萄糖苷。
• Chemoenzymatic Synthesis of β-<scp>D</scp>-Glucosides using Cellobiose Phosphorylase from<i>Clostridium thermocellum</i>
  作者：Karel De Winter、Lisa Van Renterghem、Kathleen Wuyts、Helena Pelantová、Vladimír Křen、Wim Soetaert、Tom Desmet

  DOI：10.1002/adsc.201500077

  日期：2015.5.26

  Over the past decade, disaccharide phosphorylases have been successfully applied for the synthesis of numerous α‐glucosides. In contrast, much less research has been done with respect to the production of β‐glucosides. Although cellobiose phosphorylase was already successfully used for the synthesis of various disaccharides and branched trisaccharides, its glycosylation potential towards small organic

  在过去的十年中，二糖磷酸化酶已成功地用于合成多种α-葡萄糖苷。相反，关于β-葡萄糖苷的生产的研究很少。尽管纤维二糖磷酸化酶已成功用于各种二糖和支链三糖的合成，但迄今为止尚未探索其对小的有机化合物的糖基化潜力。不幸的是，二糖磷酸化酶通常对非碳水化合物受体的亲和力很低，这促使添加溶剂。离子液体AMMOENG TM 101和乙酸乙酯被认为是最有前途的溶剂，可以合成各种β-葡萄糖苷。β- D紧接己基，庚基，辛基，壬基，癸基和十一烷基-glucopyranosides，也形成香草4- ö -β- d吡喃葡萄糖苷，2-苯乙基β- d吡喃葡萄糖苷，β-香茅β- d吡喃葡萄糖苷和1- ö -β- d吡喃葡萄糖基氢醌是由核确认磁共振波谱和质谱。此外，纤维二糖磷酸化酶的稳定性可以通过产生交联的酶聚集体而大大提高，而生物催化剂的合成辛基β- D的效率‐吡喃吡喃糖苷在辛醇上的印迹增加了一倍。后一种系统的有用性通过
• A selective and mild glycosylation method of natural phenolic alcohols
  作者：Mária Mastihubová、Monika Poláková

  DOI：10.3762/bjoc.12.51

  日期：——

  Several bioactive natural p-hydroxyphenylalkyl β-D-glucopyranosides, such as vanillyl β-D-glucopyranoside, salidroside and isoconiferin, and their glycosyl analogues were prepared by a simple reaction sequence. The highly efficient synthetic approach was achieved by utilizing acetylated glycosyl bromides as well as aromatic moieties and mild glycosylation promoters. The aglycones, p-O-acetylated arylalkyl alcohols, were prepared by the reduction of the corresponding acetylated aldehydes or acids. Various stereoselective 1,2-trans-O-glycosylation methods were studied, including the DDQ–iodine or ZnO–ZnCl₂ catalyst combination. Among them, ZnO–iodine has been identified as a new glycosylation promoter and successfully applied to the stereoselective glycoside synthesis. The final products were obtained by conventional Zemplén deacetylation.

  几种生物活性的天然p-羟基苯丙基β-D-葡萄糖苷，如香草基β-D-葡萄糖苷、沙利度苷和异云杉醇苷，以及它们的糖苷类似物，通过简单的反应序列制备。通过利用乙酰化的葡萄糖溴化物以及芳香基团和温和的糖苷化促进剂，实现了高效的合成方法。去糖基物质p-O-乙酰化芳基丙基醇是通过还原相应的乙酰化醛或酸制备的。研究了各种立体选择性的1,2-trans-O-糖基化方法，包括DDQ-碘或ZnO-ZnCl2催化剂组合。其中，ZnO-碘已被确认为一种新的糖苷化促进剂，并成功应用于立体选择性糖苷合成。最终产品通过传统的Zemplén去乙酰化获得。