allyl 3-O-benzoyl-4,6-O-benzylidene-α-D-glucopyranoside | 263550-38-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃二恶英
• 英文名称: allyl 3-O-benzoyl-4,6-O-benzylidene-α-D-glucopyranoside
• CAS: 263550-38-5
• 化学式: C₂₃H₂₄O₇
• 分子量: 412.439
• InChiKey: OLZJMMIKJIGGML-XPRTXTSQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.61
• 重原子数：
  30.0
• 可旋转键数：
  6.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.35
• 拓扑面积：
  83.45
• 氢给体数：
  1.0
• 氢受体数：
  7.0

反应信息

• 作为反应物：
  描述：

  allyl 3-O-benzoyl-4,6-O-benzylidene-α-D-glucopyranoside 在 4 A molecular sieve 、 三乙基硅基三氟甲磺酸酯 、 溶剂黄146 作用下， 以 二氯甲烷 为溶剂， 反应 6.0h， 生成
  参考文献：
  名称：

  Synthesis of sulfur analogues of methyl and allyl kojibiosides and methyl isomaltoside and conformational analysis of the kojibiosides

  摘要：

  The synthesis of methyl and allyl 5'-thio-alpha-D-kojibiosides and methyl 5'-thio-alpha-D-isomaltoside is described. The phenylselenoglycoside and trichloroacetimidate of 2,3,4,6-tetra-O-acetyl-5-thioglucose have been employed as glycosyl donors to glycosylate glucopyranosyl accepters with 2-OH and 6-OH positions free. The disaccharides thus obtained are potential glucosidase inhibitors. The conformational preferences of allyl 5'-thiokojibioside (34) were studied by comparison of experimental NOE curves with the theoretical counterparts for the corresponding methyl glycoside 25, derived from a Boltzmann-averaged grid search using the program PIMM91. Very goad agreement of experimental NOE curves derived from selective NOE measurements with the theoretical curves is found. The data are consistent with the population of a global minimum structure Phi=-43, Psi-39 degrees) to the extent of 90%, and a second local minimum (Phi=-36, Psi=-173 degrees) to the extent of 6%. An X-ray crystal structure of 34 at 190 K (R=4.2%) indicates a conformation (Phi=-46, Psi=-23 degrees) that is similar to that of the global minimum.

  DOI：

  10.1016/s0957-4166(00)80386-9
• 作为产物：
  描述：

  allyl 2,3-di-O-benzoyl-4,6-O-benzylidene-α-D-glucopyranoside 在 吡啶 、 一水合肼 作用下， 反应 24.0h， 以42%的产率得到allyl 3-O-benzoyl-4,6-O-benzylidene-α-D-glucopyranoside
  参考文献：
  名称：

  Synthesis of sulfur analogues of methyl and allyl kojibiosides and methyl isomaltoside and conformational analysis of the kojibiosides

  摘要：

  The synthesis of methyl and allyl 5'-thio-alpha-D-kojibiosides and methyl 5'-thio-alpha-D-isomaltoside is described. The phenylselenoglycoside and trichloroacetimidate of 2,3,4,6-tetra-O-acetyl-5-thioglucose have been employed as glycosyl donors to glycosylate glucopyranosyl accepters with 2-OH and 6-OH positions free. The disaccharides thus obtained are potential glucosidase inhibitors. The conformational preferences of allyl 5'-thiokojibioside (34) were studied by comparison of experimental NOE curves with the theoretical counterparts for the corresponding methyl glycoside 25, derived from a Boltzmann-averaged grid search using the program PIMM91. Very goad agreement of experimental NOE curves derived from selective NOE measurements with the theoretical curves is found. The data are consistent with the population of a global minimum structure Phi=-43, Psi-39 degrees) to the extent of 90%, and a second local minimum (Phi=-36, Psi=-173 degrees) to the extent of 6%. An X-ray crystal structure of 34 at 190 K (R=4.2%) indicates a conformation (Phi=-46, Psi=-23 degrees) that is similar to that of the global minimum.

  DOI：

  10.1016/s0957-4166(00)80386-9

文献信息

• Regioselective Benzoylation of 6-O-Protected and 4,6-O-Diprotected Hexopyranosides as Promoted by Chiral and Achiral Ditertiary 1,2-Diamines
  作者：Guixian Hu、Andrea Vasella

  DOI：10.1002/hlca.200290018

  日期：2002.12

  Monobenzoylation of triols (6-O-silylated glycopyranosides) or diols (4,6-O-benzylidenated glycopyranosides) with benzoyl chloride and triethylamine at −60° to 23° is promoted by catalytic amounts of ditertiary 1,2-diamines. The regioselectivity depends mostly on the structure of the alcohols; it is modulated by the configuration and constitution of the diamines, as shown by comparing the effect of Oriyama's

  三醇（6- Monobenzoylation ö -silylated glycopyranosides）或二醇（4,6- ö在-60℃至23 -benzylidenated glycopyranosides）与苯甲酰氯和三乙胺°通过催化量的二叔1,2-二胺的促进。区域选择性主要取决于醇的结构。通过比较Oriyama催化剂（（S）-1和（R）-1），N，N，N ′，N′-四甲基乙二胺（TMEDA ）的作用可以看出，它受二胺的构型和组成的调节。），N，N，N'，N'-四乙基乙二胺（TEEDA），Et 3 N和EtNMe 2。催化剂的空间位阻会削弱其对反应性的影响。与在Oriyama催化剂存在下外消旋-环己烷-1,2-二醇的单和二苯甲酰基化的适度对映选择性相一致，这些二胺对区域选择性的影响相当有限。尽管与过程简单相关，但是在某些情况下，这些催化剂比单一方法可产生更高的单种苯甲酸酯收率。在制备3-
• An Efficient and Regioselective Deprotection Method for Acetylated Glycosides
  作者：Jubiao Li、Yanguang Wang

  DOI：10.1081/scc-120027255

  日期：2004.1

  A new regioselective 2-O-deacetylation methodology of acetylated glycosides using 85% hydrazine hydrate in THF is described. Using this method, acetylated 1-thio-glycoside could also be selectively deprotected to give 3-O-deprotected compound.
• The Use of Diazabicyclo[2.2.2]octane as a Novel Highly Selective Dechloroacetylation Reagent
  作者：Dirk J. Lefeber、Johannis P. Kamerling、Johannes F. G. Vliegenthart

  DOI：10.1021/ol005567z

  日期：2000.3.1

  [GRAPHICS]In a study directed toward the use of the chloroacetyl protecting group in carbohydrate synthesis, the sterically hindered tertiary amine diazabicyclo[2.2.2]octane (DABCO) was found to give complete and selective cleavage of the chloroacetyl group in the presence of other ester functions such as benzoyl and acetyl groups at primary and/or secondary positions.