((2R,3S,6S)-3-acetoxy-6-cyano-3,6-dihydro-2H-pyran-2-yl)methyl acetate | 83938-00-5

• 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: ((2R,3S,6S)-3-acetoxy-6-cyano-3,6-dihydro-2H-pyran-2-yl)methyl acetate
• 英文别名: 4,6-di-O-acetyl-2,3-dideoxy-α-D-erythro-hex-2-enopyranosyl cyanide；[(2R,3S,6S)-3-acetyloxy-6-cyano-3,6-dihydro-2H-pyran-2-yl]methyl acetate
• CAS: 83938-00-5
• 化学式: C₁₁H₁₃NO₅
• 分子量: 239.228
• InChiKey: MKSMQPHODCTKEQ-GARJFASQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.2
• 重原子数：
  17
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.55
• 拓扑面积：
  85.6
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  ((2R,3S,6S)-3-acetoxy-6-cyano-3,6-dihydro-2H-pyran-2-yl)methyl acetate 生成 [(2S,6S)-6-cyano-3,6-dihydro-2H-pyran-2-yl]methyl acetate
  参考文献：
  名称：

  GREENSPOON, NOAM;KEINAN, EHUD, J. ORG. CHEM., 53,(1988) N 16, C. 3723-3731

  摘要：

  DOI：
• 作为产物：
  描述：

  1,2,3,4,6-alpha-D-葡萄糖五乙酸酯 在 N-甲基咪唑 、 4 A molecular sieve 、 氰化汞 、 溴化钛(IV) 、 铜 、 溶剂黄146 、 mercury dibromide 、 锌 作用下， 以 四氢呋喃 、 二氯甲烷 、 乙腈 为溶剂， 反应 56.0h， 生成 ((2R,3S,6S)-3-acetoxy-6-cyano-3,6-dihydro-2H-pyran-2-yl)methyl acetate
  参考文献：
  名称：

  Mild Synthesis of Disaccharidic 2,3-Enopyranosyl Cyanides and 2-C-2-Deoxy Pyranosyl Cyanides with Hg(CN)₂/HgBr₂/TMSCN

  摘要：

  Lewis acid-catalyzed dimerization of mono- and disaccharidic per-O-acetylated glycals gave di- and tetrasaccharidic O-acetylated C-glycosides, respectively. 2,3-Enopyranosyl cyanides were obtained from per-O-acetylated glycals by a new, mild anomeric S-N'-acetoxy displacement with Hg(CN)(2)/HgBr2/TMSCN. Per-O-acetylated 2-C-2-deoxy-pyranoses were converted into pyranosyl cyanides by the same reagent. An unprecedented acetic acid elimination from dimers with D-galacto- and L-fuco-configurations accompanied the S-N-displacement under those conditions. A new set of H-1 NMR coupling constants for 2,3-enopyranosyl systems was used for configurational assignment of complicated tetrasaccharide mimics.

  DOI：

  10.1021/jo0111661

文献信息

• Robust perfluorophenylboronic acid-catalyzed stereoselective synthesis of 2,3-unsaturated <i>O</i>-, <i>C</i>-, <i>N</i>- and <i>S</i>-linked glycosides
  作者：Madhu Babu Tatina、Xia Mengxin、Rao Peilin、Zaher M A Judeh

  DOI：10.3762/bjoc.15.125

  日期：——

  A convenient protocol was developed for the synthesis of 2,3-unsaturated C-, O-, N- and S-linked glycosides (enosides) using 20 mol % perflurophenylboronic acid catalyst via Ferrier rearrangement. Using this protocol, D-glucals and L-rhamnals reacted with various C-, O-, N- and S-nucleophiles to give a wide range of glycosides in up to 98% yields with mainly α-anomeric selectivity. The perflurophenylboronic

  开发了一种方便的方案，用于使用20摩尔％的全氟苯基硼酸催化剂通过Ferrier重排合成2，3-不饱和C-，O-，N-和S-连接的糖苷（烯醇）。使用该方案，D-葡糖醛酸和L-鼠李糖醛与各种C-，O-，N-和S-亲核试剂反应，以高达98％的收率（主要是α-异头异构体选择性）提供各种糖苷。全氟苯基硼酸在非常温和的反应条件下成功催化了多种底物（葡糖醛和亲核试剂）。
• Selective transformation of nitriles into amides and carboxylic acids by an immobilized nitrilase
  作者：Norbert Klempier、Anna de Raadt、Kurt Faber、Herfried Griengl

  DOI：10.1016/s0040-4039(00)92623-6

  日期：1991.1

  Using an immobilized nitrilase from Rhodococcus sp. mild and selective hydrolysis of nitriles can be achieved even in the presence of acid or base sensitive groups under neutral conditions. This method is applicable to a broad range of substrates as exemplified by aliphatic, alicyclic, heterocyclic and carbohydrate type nitriles.

  使用来自红球菌属的固定化腈水解酶。即使在中性条件下存在酸或碱敏感基团，也可以实现腈的温和选择性水解。该方法适用于各种底物，例如脂族，脂环族，杂环和碳水化合物类腈。
• Ruthenium catalyzed synthesis of 2,3-unsaturated C-glycosides from glycals
  作者：Batthula Srinivas、Thurpu Raghavender Reddy、Sudhir Kashyap

  DOI：10.1016/j.carres.2015.01.009

  日期：2015.4

  for the synthesis of 2,3-unsaturated C-glycosides. Various nucleophiles such as allyl trimethylsilane, triethylsilane, trimethylsilyl cyanide, trimethylsilyl azide and heterocycles such as thiophene and furan reacted smoothly with glycals in the presence of catalytic amount of ruthenium trichloride under mild reaction conditions.

  使用氯化钌（III）开发了一种高效且便捷的C-糖基化方法，用于合成2,3-不饱和C-糖苷。在温和的反应条件下，在催化量的三氯化钌存在下，各种亲核试剂（如烯丙基三甲基硅烷，三乙基硅烷，三甲基甲硅烷基氰化物，三甲基甲硅烷基叠氮化物）和杂环（如噻吩和呋喃）与糖类平稳地反应。
• Iodine-Catalyzed Stereoselective Synthesis of Allylglycosides, Glycosyl Cyanides and Glycosyl azides
  作者：J. S. Yadav、B. V. S. Reddy、C. Venkateshwar Rao、Pratap. K. Chand、A. R. Prasad

  DOI：10.1055/s-2001-17438

  日期：——

  Iodine efficiently catalyzes the glycosidation of glycals with allyltrimethylsilane, trimethylsilyl cyanide and trimethylsilyl azide in dichloromethane at ambient temperature to afford the corresponding 2,3-unsaturated allyl glycosides, glycosyl cyanides and glycosyl azides in excellent yields with high α-selectivity.

  碘高效催化糖烯与烯丙基三甲基硅烷、三甲基硅基氰和三甲基硅基叠氮在室温下二氯甲烷中反应，以高产率和高α-选择性得到了相应的2,3-不饱和烯丙基糖苷、糖基氰化物和糖基叠氮化合物。
• InBr3-Catalyzed Ferrier Rearrangement: An Efficient Synthesis of C-Pseudoglycals
  作者：J. S. Yadav、B. V. Subba Reddy

  DOI：10.1055/s-2002-20968

  日期：——

  Glycals react smoothly with silyl nucleophiles such as allyltrimethylsilane, trimethylsilyl cyanide and trimethylsilyl azide in the presence of a catalytic amount of indium tribromide to give the corresponding 2,3-unsaturated allyl glycosides, glycosyl cyanides and glycosyl azides in excellent yields with high α-selectivity.

  在三溴化铟的催化作用下，甘露糖碳酰化合物能够与甲硅烷类亲核试剂如烯丙基三甲基硅烷、三甲基硅氰和三甲基硅叠氮顺利反应，以优异的产率和高α-选择性得到相应的2,3-不饱和烯丙基糖苷、糖基氰化物和糖基叠氮。