methyl 6-O-benzoyl-2,3-di-O-methyl-α-D-glucopyranoside | 51517-51-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 6-O-benzoyl-2,3-di-O-methyl-α-D-glucopyranoside
• 英文别名: [(2R,3R,4S,5R,6S)-3-hydroxy-4,5,6-trimethoxyoxan-2-yl]methyl benzoate
• CAS: 51517-51-2
• 化学式: C₁₆H₂₂O₇
• 分子量: 326.346
• InChiKey: ADCMZCVXSIAMAU-SSZWKKLZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  23
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  83.4
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为产物：
  描述：

  苯甲酸苯酯 在 tetrafluoroboric acid 、 mercury(II) oxide 作用下， 反应 0.17h， 生成 methyl 6-O-benzoyl-2,3-di-O-methyl-α-D-glucopyranoside
  参考文献：
  名称：

  2-phenyl-1,3-benzodithiolylium trifluoromethanesulfonate: A reagent for the conversion of alcohols into benzyl ethers and benzoates under mild conditions.

  摘要：

  DOI：

  10.1016/s0040-4039(00)89023-1

文献信息

• Syntheses of 6-Deoxyhex-5-enopyranosides from 6-Bromo-6-deoxy- or 6-<i>O</i>-<i>p</i>-Tolylsulfonylhexopyranosides by the Use of DBU in DMSO
  作者：Ken-ichi Sato、Noriyuki Kubo、Ritsuko Takada、Shogo Sakuma

  DOI：10.1246/bcsj.66.1156

  日期：1993.4

  Various kinds of nonbranched and methyl-branched 6-deoxyhex-5-enopyranoside derivatives were prepared from 6-bromo-6-deoxy or 6-O-p-tolylsulfonylhexopyranoside in a one-pot procedure by a successive treatment with iodide anion and 1,8-diazabicyclo[5.4.0]undec-7-ene in dimethyl sulfoxide. The scope and limitations of this reaction have become apparent by observing the reactions of 18 substrates. The yields of altropyranoside and 2-deoxyribo-hexopyranoside derivatives were high, except for the 2,3-anhydropyranoside derivative. Methyl-branched 6-deoxyhex-5-enopyranoside derivatives were also obtained in practical yields.

  各种非分支和甲基分支的6-脱氧己-5-烯吡喃苷衍生物是通过将6-溴-6-脱氧或6-O-对甲苯磺酰己吡喃苷与碘离子及1,8-二氮杂双环[5.4.0]十一烯在二甲基亚砜中进行连续处理，采用一锅法制备的。通过观察18种底物的反应，这一反应的范围和局限性变得明显。除了2,3-无水吡喃苷衍生物外，其他的反应产物（如altropyranoside和2-脱氧核糖己吡喃苷衍生物）产率较高。甲基分支的6-脱氧己-5-烯吡喃苷衍生物也以实用的产率获得。
• Oxidative Cleavage of 4,6-<i>O</i>-Benzylidene Ring with t-Butyl Hydroperoxide and Copper(II) Chloride. Preparation of Methyl 4-<i>O</i>- and 6-<i>O</i>-Benzoylhexopyranoside Derivatives
  作者：Ken-ichi Sato、Tetsutaro Igarashi、Yukio Yanagisawa、Nobuya Kawauchi、Hironobu Hashimoto、Juji Yoshimura

  DOI：10.1246/cl.1988.1699

  日期：1988.10.5

  Copper(II) chloride and palladium(II) acetate were found to be highly effective catalysts for oxidative cleavage of O-benzylidene ring with t-butyl hydroperoxide. Using the former catalyst 4,6-O-benzylidenehexopyranoside derivatives were converted into the corresponding 4- and 6-benzoates in high yields. This reaction was also applicable for conversion of benzyl group into benzoyl one.

  发现氯化铜 (II) 和乙酸钯 (II) 是使用叔丁基氢过氧化物氧化裂解 O-亚苄基环的高效催化剂。使用前一种催化剂，4,6-O-亚苄基己基吡喃糖苷衍生物以高产率转化为相应的4-和6-苯甲酸酯。该反应也适用于将苄基转化为苯甲酰基。
• 2,2′-Bipyridinium chlorochromate/m-chloroperbenzoic acid-mediated cleavage of cyclic acetals to hydroxyesters
  作者：Frederick A. Luzzio、Rhiana A. Bobb

  DOI：10.1016/s0040-4039(97)00203-7

  日期：1997.3

  Benzylidene acetals are cleaved to hydroxyesters by means of a reagent system composed of 2,2′-bipyridinium chlorochromate (BPCC) and m-chloroperbenzoic acid. Oxidative cleavage of a 4,6-O-benzylidene glucose derivative affords a 6-O-benzoyl derivative.

  亚苄基缩醛的2,2'-联吡啶鎓氯铬酸盐（BPCC）组成的试剂系统的手段裂解的羟基酯和中号氯过苯甲酸。4，6-O-亚苄基葡萄糖衍生物的氧化裂解得到6-O-苯甲酰基衍生物。
• Regioselective Oxidative Cleavage of Benzylidene Acetals of Glycopyranosides with Periodic Acid Catalyzed by Tetrabutylammonium Bromide
  作者：Jean-Michel Vatèle

  DOI：10.1055/s-0033-1340056

  日期：——

  A combination of periodic acid, tetrabutylammonium bromide, and wet alumina in dichloromethane efficiently oxidized benzylidene acetals of carbohydrates to the corresponding hydroxybenzoates in excellent yields (>90%). Under these conditions, other protecting groups, such as tert-butyl(dimethyl)silyl, tert-butyl(diphenyl)silyl, and functional groups, such as epoxide, were unaffected. By varying the

  高碘酸、溴化四丁基铵和湿氧化铝在二氯甲烷中的组合有效地将碳水化合物的亚苄基缩醛氧化为相应的羟基苯甲酸酯，产率极好 (>90%)。在这些条件下，其他保护基团（例如叔丁基（二甲基）甲硅烷基、叔丁基（二苯基）甲硅烷基）和官能团（例如环氧化物）不受影响。通过改变 C3 位置保护基团的性质，获得了对 4-或 6-苯甲酸酯的良好到高的区域选择性。
• Synthesis, regioselective hydrogenolysis, partial hydrogenation, and conformational study of dioxane and dioxolane-type (9′-anthracenyl)methylene acetals of sugars
  作者：Zsolt Jakab、Attila Mándi、Anikó Borbás、Attila Bényei、István Komáromi、László Lázár、Sándor Antus、András Lipták

  DOI：10.1016/j.carres.2009.09.007

  日期：2009.12

  ring-opening reaction of the endo isomer of the methyl 2,3-O-(9'-anthracenyl)methylene-alpha-L-rhamnopyranoside took place with complete selectivity resulting in the axial (9'-anthracenyl)methyl ether, whereas a 1:1 mixture of the axial and equatorial ethers was formed upon the same reaction of the exo isomer. Catalytic hydrogenation of the sugar acetals resulted in (9',10'-dihydro-9'-anthracenyl)methylene

  甲基2,3-二-O-甲基-α-D-吡喃葡萄糖苷的二恶烷型（9'-蒽基）亚甲基缩醛用LiAlH（4）/ AlCl（3）（3：1）或Na（CN）裂解BH（3）-HCl区域选择性地分别提供4-或6-O-（9'-蒽基）甲基醚。二氧戊环型乙缩醛的外向异构体和内向异构体的氢解反应被证明是由乙缩醛碳的构型以及相邻的游离羟基的分子内参与引起的。2,3-O-（9'-蒽基）甲基-甲基-α-L-鼠李糖吡喃糖苷的内异构体的开环反应完全选择性地产生了轴向（9'-蒽基）甲基醚，而在外型异构体的相同反应下，形成了轴向和赤道醚的1：1混合物。糖缩醛的催化加氢导致（9' ，10′-二氢-9′-蒽基）亚甲基衍生物而不会影响缩醛中心。进行了高温分子动力学模拟和DFT（密度泛函理论）几何优化，以研究二恶烷型（9'，10'-dihydro-9'-蒽基）亚甲基缩醛的构象。