3,4,6-tri-O-acetyl-1,2-O-<1-(cyano)ethylidene>-α-D-galactopyranose | 52443-08-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氧吡喃
• 英文名称: 3,4,6-tri-O-acetyl-1,2-O-<1-(cyano)ethylidene>-α-D-galactopyranose
• 英文别名: [(3aR,5R,6S,7S,7aR)-6,7-diacetyloxy-2-cyano-2-methyl-5,6,7,7a-tetrahydro-3aH-[1,3]dioxolo[4,5-b]pyran-5-yl]methyl acetate
• CAS: 52443-08-0
• 化学式: C₁₅H₁₉NO₉
• 分子量: 357.317
• InChiKey: KKCSJTRPBSCHFU-VGSCMHHQSA-N

物化性质

• 沸点：
  467.1±45.0 °C(Predicted)
• 密度：
  1.35±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：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  130
• 氢给体数：
  0
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  3,4,6-tri-O-acetyl-1,2-O-<1-(cyano)ethylidene>-α-D-galactopyranose 、 N-9-fluorenylmethoxycarbonyl-O-trityl-L-serine benzyl ester 在 Cl⁽³⁾HO₄ 作用下， 以 二氯甲烷 为溶剂， 反应 5.0h， 以57%的产率得到N-9-fluorenylmethoxycarbonyl-O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-L-serine benzyl ester
  参考文献：
  名称：

  Direct glycosylation of protected O-tritylserine esters and oligopeptides

  摘要：

  N-Finoc-3-O-Tr-L-serine methyl and benzyl esters, as well as a tripeptide FmocAlaSeI(Tr)GlyOBn were directly glycosylated by 3,4,6-tri-O-acetyl-1,2-O-(1-cyanoethylidene)-alpha-D-galactopyranose in the presence of TrClO(4) in dichloromethane, yielding 32-57% of N-Fmoc-3-O-(2,3,4,6-tetra-O-acetyl-beta-D-galactopyranosyl)-L-serine esters and the corresponding tripeptide.

  DOI：

  10.1016/0008-6215(95)00097-d
• 作为产物：
  描述：

  氰化钾 、 2,3,4,6-四乙酰氧基-alpha-D-吡喃糖溴化物 在 四丁基溴化铵 、 水 作用下， 生成 3,4,6-tri-O-acetyl-1,2-O-<1-(cyano)ethylidene>-α-D-galactopyranose
  参考文献：
  名称：

  改进了一些过氧乙酰化的醛-己二吡喃并氨基氰化物的制备方法。

  摘要：

  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

  DOI：

  10.1016/s0008-6215(00)90029-6

文献信息

• 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
• The effect of high pressure on the stereospecificity of the glycosylation reaction
  作者：Nikolay K. Kochetkov、Victor M. Zhulin、Evgeny M. Klimov、Nelly N. Malysheva、Zinaida G. Makarova、Andrej Ya. Ott

  DOI：10.1016/0008-6215(87)80133-7

  日期：1987.7

  a pressure of 1.4 GPa and room temperature, the glycosylation of trityl ethers by 1,2-O-cyanoethylidene derivatives of sugars, and the polycondensation of the proper monomers in dichloromethane, proceed with absolute stereospecificity, giving rise to a 1,2-trans-glycosidic linkage, although, at the ambient pressure, the reactions studied reveal a rather low stereospecificity. The effect of high pressure

  在1.4 GPa的压力和室温下，糖的1,2-O-氰基亚乙基衍生物对三苯甲基醚的糖基化作用以及适当单体在二氯甲烷中的缩聚反应具有绝对立体定向性，从而产生1,2-反式糖苷键，尽管在环境压力下，所研究的反应显示出较低的立体特异性。高压对糖苷键形成的立体特异性的影响被解释为是由于随着压力的增加，单环糖基阳离子和双环酰基氧鎓阳离子之间的平衡向后者转移。
• An environmentally benign protocol for the synthesis of sugar 1,2-orthoesters in poly(ethylene glycol) dimethyl ether (DMPE)
  作者：Jian Yang、Shanqiao Wei、Jinzhong Zhao、Wei Zeng、Huawu Shao、Xiaofeng Ma

  DOI：10.1016/j.carres.2023.108902

  日期：2023.12

  An environmentally benign procedure has been developed for the synthesis of sugar orthoesters using anhydrous sodium acetate in poly(ethylene glycol)-dimethyl ether (DMPE). Various sugar orthoesers were prepared without using volatile organic solvent and quaternary ammonium salt. The sugar orthoesters were obtained in good to excellent yields.

  开发了一种环境友好的程序，用于在聚乙二醇二甲醚 (DMPE) 中使用无水乙酸钠合成糖原酸酯。不使用挥发性有机溶剂和季铵盐制备了各种糖原酸酯。糖原酸酯的产率良好至极好。
• Glycosylation by sugar 1,2-O-(1-cyanobenzylidene) derivatives: influence of glycosyl-donor structure and promoter
  作者：Nicolai K. Kochetkov、Vitaly I. Betaneli、Irina A. Kryazhevskikh、Andrey Ya. Ott

  DOI：10.1016/0008-6215(93)80006-z

  日期：1993.5

  3,4,6-Tri-O-acetyl-1,2-O-(1-cyanobenzylidene)-alpha-D-galactopyranoses with differently substituted aromatic nuclei have been synthesised and used as glycosyl donors in reactions with the acceptors methyl 2,3,4-tri-O-acetyl-6-O-trityl-beta-D-galactopyranoside (11) and methyl 2,4,6-tri-O-acetyl-3-O-trityl-beta-D-galactopyranoside (12). The glycosylation of 11 gave only beta products. The efficiency and stereoselectivity of the glycosylations of 12 depend on the nature of the substituent in the aromatic ring. The stereoselectivity for the formation of 1,2-trans-glycosidic bonds was the highest with the p-methoxy-benzylidene derivative with triphenylmethylium triflate as the promoter.
• Zhulin, V. M.; Klimov, E. M.; Makarov, Z. G., Doklady Chemistry, 1986, vol. 289, p. 245 - 247
  作者：Zhulin, V. M.、Klimov, E. M.、Makarov, Z. G.、Malysheva, N. N.、Kochetkov, N. K.

  DOI：——

  日期：——