2,3,4,6-tetra-O-acetyl-α-D-galactopyranosyl cyanide | 73014-31-0

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 2,3,4,6-tetra-O-acetyl-α-D-galactopyranosyl cyanide
• 英文别名: [(2R,3S,4R,5S,6R)-3,4,5-triacetyloxy-6-cyanooxan-2-yl]methyl acetate
• CAS: 73014-31-0
• 化学式: C₁₅H₁₉NO₉
• 分子量: 357.317
• InChiKey: URSBDPDTERVBDN-NIFZNCRKSA-N

物化性质

• 沸点：
  452.4±45.0 °C(Predicted)
• 密度：
  1.31±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -0.5
• 重原子数：
  25
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  138
• 氢给体数：
  0
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  2,3,4,6-tetra-O-acetyl-α-D-galactopyranosyl cyanide 在 N-溴代丁二酰亚胺(NBS) 、 过氧化氢苯甲酰 作用下， 以 四氯化碳 为溶剂， 反应 1.0h， 以88%的产率得到(2R,3R,4S,5S)-6-(乙酰氧基甲基)-2-溴-2-氰基四氢-2H-吡喃-3,4,5-三基三乙酸酯
  参考文献：
  名称：

  乙酰化C-（1-溴-d-糖基）杂环和1-溴-d-糖基氰化物的制备

  摘要：

  摘要乙酰化的C-（d-糖基）杂环与d-糖基氰化物与N-溴丁二酰亚胺在热四氯化碳或溴中的辐射下反应导致异头碳原子溴化。溴取代基的位置和这些产物的构象通过核磁共振光谱法确定。建立了溴化合物的绝对构型。

  DOI：

  10.1016/0008-6215(83)88354-2
• 作为产物：
  描述：

  D-吡喃葡萄糖 在 4-二甲氨基吡啶 吡啶 、 甲醇 、 molecular sieve 、 碘代三甲硅烷 、 三乙胺 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 、 苯 为溶剂， 反应 13.84h， 生成 2,3,4,6-tetra-O-acetyl-α-D-galactopyranosyl cyanide
  参考文献：
  名称：

  Efficient Syntheses of β-Cyanosugars Using Glycosyl Iodides Derived from Per-O-silylated Mono- and Disaccharides

  摘要：

  [GRAPHICS]Reported herein is a general method for the efficient syntheses of a variety of beta -cyano glycosides through the activation of per-O-trimethylsllyl glycosides with TMSI to form alpha -glycosyl iodides, which undergo S(N)2-type displacement when treated with tetrabutylammonium cyanide. The cyanoglycosides were reduced under mild conditions using NaBH4 in the presence of catalytic CoCl2(H2O)(6) in THF/H2O to give the corresponding aminomethyl glycosides.

  DOI：

  10.1021/ol0160405

文献信息

• Improved preparations of some per-O-acetylated aldohexopyranosyl cyanides
  作者：Robert Walter Myers、Yuan Chuan Lee

  DOI：10.1016/s0008-6215(00)90029-6

  日期：1986.10

  were readily isolated following completion of the rearrangement. It had previously been proved that reaction of 2,3,4,6-tetra-O-acetyl-alpha-D-manno- and -gluco-pyranosyl bromide with mercuric cyanide in nitromethane generates, in the ratio of approximately 1:1, the desired 1,2-trans-glycosyl cyanides and the corresponding 1,2-O-(1-cyanoethylidene) isomers (3a/b and 2a/b, respectively). Treatment of these

  3,4,6-三-O-乙酰基-1,2-O- [1-（异氰基，内氰基）亚乙基]-α-D-半乳糖-（1a / b），-α-D-葡萄糖-（2a / b）和-β-D-甘露糖吡喃糖（3a / b）分别以75％，16％和62％的产率立体异构化为相应的过O-乙酰化的1,2-反式-aldohexopyranosyl氰化物通过在干燥的硝基甲烷中用三氟化硼醚化物处理。同时获得相应的过-O-乙酰化的1,2-顺式-醛基-吡喃并吡喃糖基氰化物，产率分别为1.9、0.9和4.8％。发现过-O-乙酰基醛基己二吡喃并氨基氰化物产物对反应条件稳定，并且在重排完成后易于分离。先前已经证明，2,3,4,6-四-O-乙酰基-α-D-甘露聚糖和-葡萄糖-吡喃糖基溴化物与氰化汞在硝基甲烷中的反应生成的比率约为1：1，所需的1,2-反式-糖基氰化物和相应的1,2-O-（1-氰基亚乙基）异构体（分别为3a / b和2a / b）。在三氯甲
• Synthesis and characterization of some anomeric pairs of per-O-acetylated aldohexopyranosyl cyanides (per-O-acetylated 2,6-anhydroheptononitriles). On the reaction of per-O-acetylaldohexopyranosyl bromides with mercuric cyanide in nitromethane
  作者：Robert Walter Myers、Yuan Chuan Lee

  DOI：10.1016/0008-6215(84)85065-x

  日期：1984.9

  per-O-acetylaldohexopyranosyl cyanides of D-galactose, L-fucose, D-glucose, and D-mannose, as well as of 3,4,6-tri-O-acetyl-2-deoxy-2-phthalimido-beta-D-glucopyranosyl cyanide, are described. Cyanation of the readily available, per-O-acetylaldohexopyranosyl bromides with mercuric cyanide in nitromethane, and subsequent purification, gave the corresponding, crystalline glycosyl cyanides with a high degree of

  D-半乳糖，L-岩藻糖，D-葡萄糖和D-甘露糖以及3,4,6-三-O-乙酰-描述了2-脱氧-2-邻苯二甲酰亚胺基-β-D-吡喃葡萄糖基氰化物。在硝基甲烷中将氰化汞与现成的全-O-乙酰基醛基吡喃并吡喃糖基溴化物氰化，然后纯化，得到相应的结晶的糖基氰基氰化物，具有较高的1,2-反式立体选择性。因此，以20至79％的产率获得1,2-反式构型的全-O-乙酰化的醛-己二吡喃喃糖基氰化物，而以小于或等于8.4％的产率获得相应的1,2-顺式异构体。如此制备的1,2-反式：1,2-顺式端基异构体的比例大于或等于8.5：1。这些不可逆的氰化反应的主要副产物是全-O-乙酰化的1,2-O- [1-（异氰基和内氰基）亚乙基] aldohexopyranoses，得率高达40％。通过元素分析，化学转化，振动光谱以及13C和1H核磁共振光谱明确地确定了每个O-乙酰基乙二醛-吡喃并吡喃糖基氰化物的结构分配。描述了这些C
• Efficient synthesis of α-Aldopyranosyl cyanides via radical cyanation reactions
  作者：Jaime Martin、Luz Marina Jaramillo G、Peng George Wang

  DOI：10.1016/s0040-4039(98)01213-1

  日期：1998.8

  α-Aldopyranosylcyanides were efficiently prepared by a radical cyanation reaction between glycosyl bromides or glycosyl dithiocarbonates with tert-butylisocyanide, tris(trimethylsilyl)silane and 2,2′-azoisobutyronitriles.

  通过糖基溴化物或糖基二硫代碳酸酯与叔丁基异氰化物，三（三甲基甲硅烷基）硅烷和2,2'-偶氮异丁腈之间的自由基氰化反应，可以有效地制备α-醛基吡喃糖基氰化物。
• Preparation of 1,2--glycosyl cyanides by the stereoselective reduction of acetylated l-bromo-d-glycosyl cyanioes
  作者：Lászlo Somsák、Gyula Batta、István Farkas

  DOI：10.1016/s0040-4039(00)85352-6

  日期：1986.1

  Reductive dehalogenation of acetylated 1-bromo-D-glycosyl cyanides with tri--butyltin hydride favours the formation of 1,2--glycosyl cyanides, while reactions with zinc-acetic acid, zinc-isopropanol, and sodium borohydride give 1,2--glycosyl cyanides as the major product.

  乙酰化的1-溴-D-糖基氰化物与三-丁基锡氢化物的还原脱卤作用有利于1,2-糖基氰化物的形成，而与锌-乙酸，锌-异丙醇和硼氢化钠的反应则得到1,2- -糖基氰化物为主要产物。
• Efficient stereocontrolled synthesis of C-glycosides using glycosyl donors substituted by propane 1,3-diyl phosphate as the leaving group
  作者：Gurdial Singh、Hariprasad Vankayalapati

  DOI：10.1016/s0957-4166(01)00305-6

  日期：2001.7

  a- and beta -Glycosyl cyanides, per-O-acetyl-1,2-O-1-cyanoethylidenes and C-allyl glycopyranosides were efficiently prepared by treatment of 2,3,4-tri-O-acetyl-alpha,beta -L-rhamno-, L-fuco- and 2,3,4,6-tetra-O-acetyl-alpha,beta -D-galactopyranosyl propane-1,3-diyl phosphates with trimethylsilyl cyanide (TMSCN) and allyltrimethylsilane in the presence of trimethylsilyl triflate (TMSOTf). Similarly 2,3,4,6-tetra-O-benzyl-alpha,beta -D-manno- and D-glucopyranosyl propane-1,3-diyl phosphates were employed in the synthesis of C-glycosides. (C) 2001 Elsevier Science Ltd. All rights reserved.