2,3,4,6-tetra-O-benzyl-1-C-ethyl-α-D-glucopyranose | 255843-71-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2,3,4,6-tetra-O-benzyl-1-C-ethyl-α-D-glucopyranose
• 英文别名: (2S,3R,4S,5R,6R)-2-ethyl-3,4,5-tris(phenylmethoxy)-6-(phenylmethoxymethyl)oxan-2-ol
• CAS: 255843-71-1
• 化学式: C₃₆H₄₀O₆
• 分子量: 568.71
• InChiKey: WEDQBCXQKOPAGE-GJXDWMKPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.7
• 重原子数：
  42
• 可旋转键数：
  14
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  66.4
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  三甲基氰硅烷 、 2,3,4,6-tetra-O-benzyl-1-C-ethyl-α-D-glucopyranose 在 calcium sulfate 、 三氟甲磺酸三甲基硅酯 作用下， 以 乙腈 为溶剂， 反应 3.0h， 以90%的产率得到(2R,3R,4S,5R,6R)-3,4,5-tris(benzyloxy)-6-(benzyloxy)methyl-2-ethyltetrahydropyran-2-carbonitrile
  参考文献：
  名称：

  Trimethylsilyl Trifluoromethanesulfonate Catalyzed Nucleophilic Substitution To Give C- and N-Glucopyranosides Derived from d-Glucopyranose

  摘要：

  本文描述了通过三甲基硅基三氟甲磺酸盐催化的亲核取代反应合成C-和N-葡萄糖吡喃糖苷，该反应是通过将来自D-葡萄糖吡喃糖的葡萄糖吡喃糖苷与甲基、乙基、正丁基、烯丙基、苄基和苯基等在异头碳中心进行的。通常，在-40°C时，在20摩尔%的三甲基硅基三氟甲磺酸盐存在下，使用烯丙基三甲基硅烷、三甲基硅基叠氮化物、三甲基硅基氰化物和1-苯基-1-(三甲基硅氧基)乙烯作为亲核试剂的反应顺利进行，并表现出α立体选择性，产率在78-99%之间。尽管对于某些使用含有烯丙基和苄基的葡萄糖吡喃糖在异头碳的反应观察到了合成产率的下降，但在-78°C的氯乙烯-二氯甲烷（1:1）混合物中使用葡萄糖吡喃糖醋酸酯并在存在20摩尔%三甲基硅基三氟甲磺酸盐的条件下，产率可以得到改善。

  DOI：

  10.1055/s-2007-983882
• 作为产物：
  描述：

  5-内酯 、 三乙基铝 以 二氯甲烷 为溶剂， 反应 3.0h， 以69%的产率得到2,3,4,6-tetra-O-benzyl-1-C-ethyl-α-D-glucopyranose
  参考文献：
  名称：

  Addition of trialkylaluminum reagents to glyconolactones. Synthesis of 1-C-methyl GlcNAc oxazoline and thiazoline

  摘要：

  Addition of carbon nucleophiles to 2-acetamido-2-deoxygluconolactones fails for many reagents, but trialkylaluminums add alkyl smoothly. The product of Methyl addition to 2-acetamido-2-deoxy-D-gluconolactone has been converted to 1-C-methyl GlcNAc thiazoline, a potential N-acetylhexosaminidase inhibitor, and to an O-protected I-C-Me GlcNAc oxazoline, a potential I-C-Me GlcNAc donor. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(02)01506-x

文献信息

• Synthesis of 1-C-alkyl-α-d-glucopyranosides by Lewis acid- or Brønsted acid-catalyzed O-glycosidation
  作者：Takashi Yamanoi、Yoshiki Oda、Sho Matsuda、Ippo Yamazaki、Kazuhide Matsumura、Kaname Katsuraya、Mikio Watanabe、Toshiyuki Inazu

  DOI：10.1016/j.tet.2006.08.059

  日期：2006.10

  donors to synthesize 1-C-alkyl-d-glucopyranosides were investigated. Using 10 mol % of triphenylmethyl perchlorate efficiently catalyzed the glycosidation of 2,3,4,6-tetra-O-benzyl-1-C-methyl-α-d-glucopyranosyl dimethylphosphinothioate. The glycosidation using the 1-C-alkyl-2,3,4,6-tetra-O-benzyl-α-d-glucopyranosyl acetates smoothly proceeded in the presence of only 5 mol % of scandium(III) trifluoromethanesulfonate

  我们制备了几种1- C-烷基-2,3,4,6-四-O-苄基-α-d-吡喃葡萄糖衍生物，它们的端基均含有甲基，乙基，正丁基和苄基作为烷基职位。研究了路易斯酸或布朗斯台德酸催化的O-糖基化反应，将其用作糖基供体以合成1- C-烷基-d-吡喃葡萄糖苷。使用10mol％的高氯酸三苯甲基酯有效地催化了2,3,4,6-四-O-苄基-1- C-甲基-α-d-吡喃葡萄糖基二甲基硫代磷酸酯的糖基化。使用1- C-烷基-2,3,4,6-四-O的糖基化在仅5mol％的三氟甲磺酸scan（III）的存在下，-苄基-α-d-吡喃葡萄糖基乙酸酯平稳地进行。使用5 mol％的双（三氟甲烷）磺酰亚胺，可显着促进使用1- C-烷基-2,3,4,6-四-O-苄基-α-d-吡喃葡萄糖的脱水-缩合型糖基化作用。这些糖苷化以高收率和高α-立体选择性成功地提供了各种1- C-烷基-α-d-吡喃葡萄糖苷。
• Synthesis of glycosyl boranes and glycosyl borinates†
  作者：Andrea Vasella、Wolfgang Wenger、Thennati Rajamannar

  DOI：10.1039/a906400a

  日期：——

  Insertion of glycosylidene carbenes into a B–C bond of BEt3 leads to unstable glycosyl boranes, while insertion into a B–C bond of borinic esters yields stable anomeric glycosyl borinates.

  将糖苷烯碳烯插入BEt3的B–C键，产生不稳定的糖苷硼烷；而将其插入硼酸酯的B–C键，则形成稳定的差向糖苷硼酸盐。
• The Brfnsted Acid-catalyzed O-Glycosidation of 1-C-Alkyl-D-glucopyranose Derivatives
  作者：Takashi Yamanoi、Sho Matsuda、Ippo Yamazaki、Ryo Inoue、Keita Hamasaki、Mikio Watanabe

  DOI：10.3987/com-06-10684

  日期：——

  We found that the O-glycosidation between various kinds of 1-C-alkyl-2,3,4,6-tetra-O-benzyl-D-glucopyanoses and alcohols in the presence of 5 mol % of trifluoromethanesulfonic acid or bis(trifluoromethane)sulfonimide stereoselectively produced the corresponding 1-C-alkyl-alpha-D-glucopyranosides in good yields.
• Glycosylidene Carbenes, Part 29 , Insertion into B−C and Al−C Bonds: Glycosylborinates, -boranes, and -alanes
  作者：Wolfgang Wenger、Andrea Vasella

  DOI：10.1002/1522-2675(20000705)83:7<1542::aid-hlca1542>3.0.co;2-f

  日期：2000.7.5

  Insertion of the glycosylidene carbenes derived from the diazirines 1, 14 and 15 into the B-alkyl bond of the B-alkyl-9-oxa-10-borabicyclo[3.3.2]decanes 5, 6, and 7 yielded the stable glycosylborinates 8/9 (55%, 55:45), 10/11 (31%, 65:35), 12/13 (47%, 60:40), 16/17 (55%, 55:45), 18/19 (47%, 45:55), and 20/21 (31%, 30:70). Crystal-structure analysis of 17 and NOEs of 9 and 19 show that 17 9, and 19 adopt similar conformations. The glycosylborinates are stable under acidic, basic and thermal conditions. The unprotected glycosylborinate 25 was obtained in 80% by hydrogenolysis of 12. Insertion of the glycosylidene carbene derived from the diazirine 1 into a B-C bond of BEt3, BBu3, and BPh3 led to unstable glycosylboranes that were oxidised to yield the hemiacetals 29 (55%), 31 (45%), and 33 (48%), respectively, besides the glucals 30 (13%), 32 (20%), and 34 (20%), respectively. Insertion of the glycosylidene carbenes derived from 14 and 15 into a B - C bond of BEt3 led exclusively to hemiacetals; only 15 yielding traces of the glucal 40 besides the hemiacetal 39. The glycosylidene carbene derived from 1 reacted with AL(Bu-1), and AlMe3 to generate reactive glycosylalanes that were hydrolysed, yielding the C-glycosides 46 (21%) and 49 (30%), respectively besides the glucals 48 (26%) and 51 (30%); deuteriolysis instead of protonolysis led to the monodeuterio analogues of 46 and 49, respectively, which possess an equatorial H-2-atom at the anomeric center.