3,4,6-tri-O-acetyl-1,2-O-<1-(endo-cyano)-ethylidene>-α-D-galactopyranose | 69927-14-6

• 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-(endo-cyano)-ethylidene>-α-D-galactopyranose
• 英文别名: 3,4,6-tri-O-acetyl-1,2-O-[1-(endo-cyano)-ethylidene]-α-D-galactopyranose；3,4,6-tri-O-acetyl-1,2-O-[1-(endo-cyano)ethylidene]-α-D-galactopyranose；3,4,6-tri-O-acetyl-1,2-O-(R)-(1-cyano-ethylidene)-α-D-galactopyranose；[(2R,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: 69927-14-6
• 化学式: C₁₅H₁₉NO₉
• 分子量: 357.317
• InChiKey: KKCSJTRPBSCHFU-YXJLRHLOSA-N

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-(endo-cyano)-ethylidene>-α-D-galactopyranose 在 Jones reagent 、 碳酸氢钠 作用下， 反应 1.5h， 生成 methyl 3,4-di-O-acetyl-1,2-O-<1-(endo-cyano)ethylidene>-α-D-galactopyranuronate
  参考文献：
  名称：

  通过氧化己糖类似物的6-三苯甲基醚来合成烷基吡喃葡萄糖酸酯的1，2-O-氰基亚乙基衍生物

  摘要：

  摘要通过氧化3,4-二-O-乙酰基-6，描述了具有d -Glc，d -Gal和d -Man构型的吡喃葡萄糖醛酸烷基酯的1,2-O-氰基亚乙基衍生物（CED）的合成。 -O-三苯甲基-CED-己糖类似物与琼斯试剂[氧化铬（VI）-硫酸]。证明了含羟基的三苯基甲基醚的异丙基化。

  DOI：

  10.1016/0008-6215(88)84108-9
• 作为产物：
  描述：

  三甲基氰硅烷 、 propane-1,3-diyl 2,3,4,6-tetra-O-acetyl-α,β-D-galactopyranosyl phosphate 在 三氟甲磺酸三甲基硅酯 作用下， 以 二氯甲烷 为溶剂， 反应 0.5h， 以53%的产率得到3,4,6-tri-O-acetyl-1,2-O-<1-(exo-cyano)ethylidene>-α-D-galactopyranose
  参考文献：
  名称：

  Efficient stereocontrolled synthesis of C-glycosides using glycosyl donors substituted by propane 1,3-diyl phosphate as the leaving group

  摘要：

  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.

  DOI：

  10.1016/s0957-4166(01)00305-6

文献信息

• Different reactivities of acetylated exo- and endo-cyanoethylidene derivatives in glycosylation reactions
  作者：Cristina Vicent、Jose-Miguel Coteron、Jesus Jimenez-Barbero、Manuel Martin-Lomas、Soledad Penades

  DOI：10.1016/0008-6215(89)85016-5

  日期：1989.12

  Abstract The condensation of acetylated 1-( endo -cyano)ethylidene derivatives having the d - gluco , d - xylo , and d - galacto configurations ( 2 – 6 ) with a primary ( 8 ) and a secondary ( 9 ) trityl derivative was more rapid than for the corresponding exo -isomers. This difference in reactivity is explained on the basis of differences in conformation.

  摘要具有d-葡萄糖，d-木糖和d-半乳糖构型（2-6）与伯（8）和仲（9）三苯甲基衍生物的乙酰化1-（内氰基）亚乙基衍生物的缩合反应较多。比相应的exo-异构体快。反应性的差异是根据构象差异来解释的。
• Unusual regioselective glycosylation of sugar secondary trityloxy function in the presence of primary one
  作者：Yury E. Tsvetkov、Pavel I. Kitov、Leon V. Backinowsky、Nikolay K. Kochetkov

  DOI：10.1016/s0040-4039(00)61529-0

  日期：1993.12

  Primary-secondary sugar ditrityl ethers are selectively glycosylated at the secondary position
• Reactivity of 1,2-O-cyanoalkylidene sugar derivatives in trityl-cyanoalkylidene condensation
  作者：P. I. Kitov、Yu. E. Tsvetkov、L. V. Backinowsky、N. K. Kochetkov

  DOI：10.1007/bf00699947

  日期：1993.8

  The rate-determining step of trityl-cyanoalkylidene condensation is the interaction between the cyanoalkylidene derivative (CD) and the triphenylmethyl cation. The rate of the reaction follows first-order kinetics with respect to both CD and the catalyst (Tr+) and is independent of the nature and concentration of the trityl ether. Glycosylation rate constants have been determined for CD's of most common monosaccharides.
• The cyanation reaction of O-acetylated S-glycosyl phosphorothioates
  作者：Wiesława Kudelska

  DOI：10.1016/s0008-6215(00)00216-0

  日期：2000.11

  The reaction of alpha- and beta -1-S-phosphorothioates of per-O-acetylated monosaccharides (galactose, xylose, glucose) with trimethylsilyl cyanide in the presence of boron trifluoride etherate has been investigated. It has been established that in dichloromethane 1,2-O-cyanoethylidene derivatives of aldoses are formed in high yields. When the reaction was carried out in acetonitrile, peracetylated galactosyl cyanide was formed as the major product. (C) 2000 Elsevier Science Ltd. All rights reserved.
• Reactivity of sugar trityl ethers in trityl?cyanoalkylidene condensation
  作者：P. I. Kitov、Yu. E. Tsvetkov、L. V. Backinowsky、N. K. Kochetkov

  DOI：10.1007/bf00699016

  日期：1993.11

  The reactivity of a series of primary and secondary sugar trityl ethers in trityl-cyanoalkylidene condensation has been determined. It was found that the stereoselectivity of glycosylation by this method does not directly depend on the reactivity of the trityl ethers. Based on the results obtained, a stepwise mechanism rather than a concerted mechanism has been chosen as the most probable.