2,3,4,6-tetra-O-benzyl-α-D-glucopyranosyl cyanide | 71119-79-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2,3,4,6-tetra-O-benzyl-α-D-glucopyranosyl cyanide
• 英文别名: (2R,3S,4R,5R,6R)-3,4,5-tris(phenylmethoxy)-6-(phenylmethoxymethyl)oxane-2-carbonitrile
• CAS: 71119-79-4
• 化学式: C₃₅H₃₅NO₅
• 分子量: 549.667
• InChiKey: MSKBHSHLODZBHV-CKQPALCZSA-N

物化性质

• 沸点：
  693.0±55.0 °C(Predicted)
• 密度：
  1.20±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.3
• 重原子数：
  41
• 可旋转键数：
  13
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  69.9
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  2,3,4,6-tetra-O-benzyl-α-D-glucopyranosyl cyanide 在 吡啶 、 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 为溶剂， 反应 1.0h， 生成 N-((2R,3S,4R,5R,6R)-3,4,5-Tris-benzyloxy-6-benzyloxymethyl-tetrahydro-pyran-2-ylmethyl)-acetamide
  参考文献：
  名称：

  Recognition Properties of Processing α‐Glucosidase I and α‐Glucosidase II

  摘要：

  All four possible monodeoxy derivatives of p-nitrophenyl alpha-D-glucopyranoside (PNP Glc) and 1-amino-2,6-anhydro-1-deOXY-D-glycero-D-ido-heptitol derivatives were prepared and used as substrates and inhibitors of rat liver processing alpha-glucosidases. alpha-Glucosidase II hydrolyzed the 2-deoxy derivative of PNP Glc (1); the hydrolysis of 1 was more rapid than that of PNP Glc. These results indicate that the presence of a C-2 hydroxyl group is not essential for the action of alpha-glucosidase II. In contrast, PNP Glc and all of the deoxy derivatives of PNP Glc 1-4 inhibited alpha-glucosidase I. These results indicate that alpha-glucosidase I does not necessarily need all of the hydroxyl groups of the glycon moiety for binding to the enzyme. 2,6-Anhydro-1-benzamide-D-glycero-D-ido-heptitol (11), with a terminal phenyl group, inhibited a-glucosidase I and a-glucosidase II. Both alpha-glucosidase I and II showed the same aglycon specificities. When probes 5-12 were assayed for their ability to inhibit processing by a-glucosidases at the cellular level, no effects on glycoprotein processing were observed.

  DOI：

  10.1081/car-120030022
• 作为产物：
  描述：

  2,3,4,6-四苄基-D-吡喃葡萄糖 在 zinc trifluoromethanesulfonate 、 三乙胺 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 1.0h， 生成 2,3,4,6-tetra-O-benzyl-α-D-glucopyranosyl cyanide
  参考文献：
  名称：

  在Glycopyranosyl氰化物中添加有机锌试剂：获得Keto Ester-C-glycosides或不饱和的Acyl-C-glycosides

  摘要：

  通过将Reformatsky型或烯丙基锌试剂添加到2,3,4,6中的反应，已在半乳糖，葡萄糖和甘露糖系列中以中等至极高的收率制备了原始的酮酯C-糖苷或不饱和酰基C-糖苷。 -四-O-苄基甘露糖基氰化物。

  DOI：

  10.1002/ejoc.201800090

文献信息

• A general approach to C-Acyl glycosides via palladium/copper Co-catalyzed coupling reaction of glycosyl carbothioates and arylboronic acids
  作者：Li-Na Wang、You-Hong Niu、Qing-Hui Cai、Qin Li、Xin-Shan Ye

  DOI：10.1016/j.tet.2021.131955

  日期：2021.2

  A general and efficient approach to the synthesis of various C-acyl glycosides has been developed via Pd2(dba)3/CuTC co-catalyzed cross-coupling reaction of glycosyl carbothioates with arylboronic acids. The reaction showed a broad substrate scope and 25 examples were exhibited in 61%–97% isolated yields. Furthermore, this reaction was applied to the gram-scale preparation of C-acyl glycosides. The

  通过Pd 2（dba）3 / CuTC共催化的糖基硫代糖基酸酯与芳基硼酸的交叉偶联反应，已经开发了一种合成各种C-酰基糖苷的通用有效方法。该反应显示出较宽的底物范围，其中25个实例的分离产率为61％–97％。此外，该反应被用于克规模的C-酰基糖苷的制备。偶联的产物可以进一步转化为多种生物学上有用的化合物，例如通过合成保护的Sergliflozin-A模拟物。
• Improved preparation of 4(5)-aryl-2-(β-<scp>d</scp>-glucopyranosyl)-imidazoles, the most efficient glucose analogue inhibitors of glycogen phosphorylase
  作者：Eszter Szennyes、Éva Bokor、Gyula Batta、Tibor Docsa、Pál Gergely、László Somsák

  DOI：10.1039/c6ra21839c

  日期：——

  currently most efficient glucose derived inhibitors of glycogen phosphorylase enzymes was amended and extended by using O-perbenzylated β-D-glucopyranosyl cyanide as the starting material. This compound and its derivatives C-(β-D-glucopyranosyl)formimidate and formamidine were obtained in large scale reactions to give the products in ∼20 grams amounts. Ring closing reactions of the formimidate and formamidine

  通过使用O-过苄基化的β- D-吡喃葡萄糖基氰化物作为邻苯二甲酸酯，对目前最有效的葡萄糖衍生的糖原磷酸化酶抑制剂的4（5）-芳基-2-（β- D-吡喃葡萄糖基）-咪唑的合成进行了改进和扩展。起始材料。通过大规模反应获得了该化合物及其衍生物C-（β- D-吡喃葡萄糖基）甲酸酯和甲am，得到的产物约为20克。甲亚氨酸和甲am分别通过α-氨基和α-溴代酮的闭环反应产生了O-过苄基化的咪唑，其通过催化氢化或通过EtSH / BF 3 ·OEt 2脱保护。。新制备的4（5） - （4-硝基-和氨基苯基）-2-（β- d吡喃葡萄糖基） -咪唑证明效率较低的抑制剂（ķ我值分别为1141和411纳米，）比它们的未取代的对应物（ķ i = 280 nM）。
• Reactions of glycosyl fluorides. Synthesis of C-glycosides
  作者：K. C. Nicolaou、Roland E. Dolle、Alexander Chucholowski、Jared L. Randall

  DOI：10.1039/c39840001153

  日期：——

  Glycosyl fluorides were found to react with a number of nucleophilic reagents with or without catalysis leading to a variety of C-glycosides and related compounds.

  发现糖基氟化物在催化作用或不催化作用下与许多亲核试剂反应，从而导致多种C-糖苷和相关化合物。
• Preparation of 1-C-glycosyl aldehydes by reductive hydrolysis
  作者：Szabolcs Sipos、István Jablonkai

  DOI：10.1016/j.carres.2011.04.019

  日期：2011.9

  carried out using DIBAL-H to form aldimine alane intermediates which were then hydrolyzed under mildly acidic condition to provide the corresponding aldehyde derivatives. While 1-C-formyl glycal and 2-deoxy glycosyl derivatives were stable during isolation and storage 1-C-glycosyl formaldehydes in the gluco, galacto and manno series were sensitive and decomposition occurred by 2-alkyloxy elimination

  使用DIBAL-H进行各种保护的糖基氰化物的还原水解以形成醛亚胺铝烷中间体，然后将其在中等酸性条件下水解以提供相应的醛衍生物。尽管1-C-甲酰基糖基和2-脱氧糖基衍生物在分离和存储过程中是稳定的，但葡萄糖，半乳糖和甘露糖系列中的1-C-糖基甲醛很敏感，并且通过2-烷氧基消除发生了分解。开发了一种使用N，N'-二苯基乙二胺以稳定形式捕集这些醛的一锅法。糖基氰化物的还原水解以方便的方式提供了有价值的醛结构单元，可用于合成复杂的C-糖苷。
• Synthesis of Glycosyl Cyanides by the Reaction of 1-S-Phosphorothioates of Carbohydrates with Trimethylsilyl Cyanide
  作者：Wieslawa Kudelska

  DOI：10.1515/znb-1998-1107

  日期：1998.11.1

  A new procedure is described for the synthesis of α,β-glycosyl cyanides by the reaction of per-O-benzylated S-α-ᴅ-glycopyranosyl phosphorothioates with trimethylsilyl cyanide in the presence of Lewis acid. Starting S-glycosyl phosphorothioates are prepared, directly, from O-benzyl protected reducing D-hexopyranoses (gluco-, galacto-, manno-) and alkylammonium salt of phosphorothioic acid under Lewis

  在路易斯酸的存在下，通过 per-O-苄基化 S-α-ᴅ-吡喃糖基硫代磷酸酯与三甲基甲硅烷基氰化物的反应，描述了一种合成 α,β-糖基氰化物的新方法。在路易斯酸催化下，从 O-苄基保护的还原性 D-吡喃己糖（葡萄糖-、半乳糖-、甘露糖-）和硫代磷酸的烷基铵盐直接制备起始 S-糖基硫代磷酸酯。