methyl 4-O-benzoyl-6-bromo-6-deoxy-2,3-di-O-methyl-α-D-glucopyranoside | 56543-17-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 4-O-benzoyl-6-bromo-6-deoxy-2,3-di-O-methyl-α-D-glucopyranoside
• 英文别名: α-methyl-6-bromo-4-benzyl ester-2,3-di-O-methyl-D-glucopyranoside；methyl 4-O-benzoyl-6-bromo-6-deoxy-2,3-di-O-methyl-α-D-glucoside；[(2S,3S,4S,5R,6S)-2-(bromomethyl)-4,5,6-trimethoxyoxan-3-yl] benzoate
• CAS: 56543-17-0
• 化学式: C₁₆H₂₁BrO₆
• 分子量: 389.243
• InChiKey: LZBKZDFTJDSWJW-SSZWKKLZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 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：
  63.2
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  methyl 4-O-benzoyl-6-bromo-6-deoxy-2,3-di-O-methyl-α-D-glucopyranoside 在 sodium hydroxide 、 sodium tetrahydroborate 作用下， 以 乙醇 、 水 、 二甲基亚砜 为溶剂， 反应 5.0h， 生成 methyl 6-deoxy-2,3-di-O-methyl-α-D-glucopyranoside
  参考文献：
  名称：

  α-d-己基吡喃糖苷-4-酮与重氮甲烷反应的立体选择性

  摘要：

  摘要比较了重氮甲烷与各种α-d-己基吡喃糖苷-4-纤维素反应的立体选择性和格氏反应中的立体选择性。该结果支持以下假设：重氮甲烷反应的立体选择性主要受重氮甲基阳离子与过渡态中O-5的相邻轴向氧或轴向孤对电子之间的吸引力，静电力控制。

  DOI：

  10.1016/s0008-6215(00)80685-0
• 作为产物：
  描述：

  methyl 4,6-O-benzylidene-2,3-di-O-methyl-α,D-glucopyranoside 在 N-溴代丁二酰亚胺(NBS) 、 calcium carbonate 作用下， 以 四氯化碳 为溶剂， 以90%的产率得到methyl 4-O-benzoyl-6-bromo-6-deoxy-2,3-di-O-methyl-α-D-glucopyranoside
  参考文献：
  名称：

  Formation of septanoses from hexopyranosides via 5,6-exo-glycals

  摘要：

  Methyl D-hexo-5-ulosides are obtained in high yield by dihydroxylation of 5,6-exo-glucal compounds. The bicyclic structure (1,6-anhydropyrano-5-ulose) of the products is adopted in solution and in solid state in a C-4(1) conformation. This methodology has been used to prepare 1,6-anhydro-L-idopyrano-5-uloses. Further manipulation of the 1,6-anhydro bridge allowed the preparation of the yet unknown septano-5-uloses in moderate to high yields. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.carres.2012.02.026

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。
• Chain elongation by use of an iron carbonyl reagent: A facile synthesis of 6-deoxyheptosiduronic acids
  作者：Hans H. Baer、Hanna R. Hanna

  DOI：10.1016/s0008-6215(00)88060-x

  日期：1982.4

  tosyloxy group was replaced by the Fp group. Oxidative carbonyl insertion in 2 could be induced by a variety of oxidants, but was best accomplished by bromine in the presence of methanol, at low temperatures. The process caused removal of the iron moiety, and led, in 80% overall yield, to the methyl ester of the corresponding, 6-deoxyheptosid-uronic acid. Similarly, the methyl 4- O -benzoyl-6-bromo-6-deoxy-α-

  摘要在有机铁化学的基础上，发展了一种在6-脱氧-6-卤代和6-O-甲苯磺酰基-己吡喃糖苷的非还原性末端进行链延长的方法，以制得（甲基6-脱氧庚基吡喃糖苷）尿酸甲酯。因此，甲基2,3,4-三-O-乙酰基-6-O-对甲苯磺酰基-β-d-吡喃葡萄糖苷在温和的条件下几乎立即与在氧戊烷中的二羰基-η5-环戊二烯基铁（NaFp）反应形成一种可分离的，表征良好的铁衍生物（2），其中甲苯磺酰氧基被Fp基团取代。各种氧化剂均可诱导2中的羰基氧化插入，但最好在低温下在甲醇存在下用溴完成。该方法引起铁部分的除去，并以80％的总产率导致产生相应的6-脱氧庚糖苷-尿醛酸的甲酯。
• Hydrophobic, Hydrophilic, and Amphiphilic Polyglycocarbonates with Linear and Macrocyclic Architectures from Bicyclic Glycocarbonates Derived from CO₂ and Glucoside
  作者：Debasis Pati、Xiaoshuang Feng、Nikos Hadjichristidis、Yves Gnanou

  DOI：10.1021/acs.macromol.6b02527

  日期：2017.2.28

  other hand, macrocyclic polyglycocarbonate homopolymers and diblock copolymers were grown using 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) which served as zwitterionic initiator. The various architectures derived were all thoroughly characterized by NMR, GPC, and MALDI-tof and shown to exhibit the expected structure. Finally, the self-assembly of linear and macrocyclic amphiphilic copolyglycocarbonates

  两个双环glycocarbonates在从α甲基五步合成d葡糖苷不诉诸光气或它的衍生物的第一次。使用CO 2修饰葡萄糖的4位和6位以引入六元碳环作为羰基化试剂；首先将同一葡糖苷底物的2位和3位转化为甲基或三甘醇单甲醚基团，以保护这些位置免受不良反应的影响，并且在第一种情况下赋予疏水性，在第二种情况下赋予亲水性。然后在不同条件下研究了这些双环碳酸酯的聚合行为。一方面，通过上述单体的开环聚合，由p引发的线性聚碳酸碳酸酯均聚物和二嵌段共聚物被获得。-甲基苄醇，使用1,5,7-三氮杂双环[4.4.0] dec-5-ene（TBD）作为催化剂；另一方面，使用作为两性离子引发剂的1,8-二氮杂双环[5.4.0]十一碳-7-烯（DBU）来生长大环聚碳酸酯碳酸酯均聚物和二嵌段共聚物。通过NMR，GPC和MALDI-tof对衍生的各种结构进行了全面表征，并显示出预期的结构。最后，研究了线性和大环两亲共聚碳酸
• Convenient Synthesis of Hex-5-enopyranosides
  作者：Ken-ichi Sato、Noriyuki Kubo、Rituko Takada、Amjad Aqeel、Hironobu Hashimoto、Juji Yoshimura

  DOI：10.1246/cl.1988.1703

  日期：1988.10.5

  Hex-5-enopyranosides were prepared in an one-pot procedure from 6-bromo-6-deoxy- or 6-O-tosylhexopyranoside by the successive treatment with iodide anion and 1,8-diazabicyclo-[5.4.0]undec-7-ene in DMSO.

  通过在二甲基亚砜中连续处理碘离子和1,8-二氮杂双环[5.4.0]十一碳-7-烯，以一锅法从6-溴-6-脱氧-或6-O-对甲苯磺酰基己吡喃糖苷制备了六-5-烯吡喃糖苷。
• Metal-graphite reagents in carbohydrate chemistry. 8. The scope and limitations of the use of zinc/silver-graphite in the synthesis of carbohydrate-derived substituted hex-5-enals and pent-4-enals
  作者：Alois Fuerstner、Denis Jumbam、Judith Teslic、Hans Weidmann

  DOI：10.1021/jo00006a047

  日期：1991.3