methyl 2,3,6-tri-O-benzyl-4-O-(1H-imidazol-1-ylsulfonyl)-α-D-galactopyranoside | 432038-84-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 2,3,6-tri-O-benzyl-4-O-(1H-imidazol-1-ylsulfonyl)-α-D-galactopyranoside
• 英文别名: [(2R,3S,4R,5R,6S)-6-methoxy-4,5-bis(phenylmethoxy)-2-(phenylmethoxymethyl)oxan-3-yl] imidazole-1-sulfonate
• CAS: 432038-84-1
• 化学式: C₃₁H₃₄N₂O₈S
• 分子量: 594.686
• InChiKey: CSVDVHJLFLXGCZ-NBCLCUQJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  42
• 可旋转键数：
  14
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  116
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  methyl 2,3,6-tri-O-benzyl-4-O-(1H-imidazol-1-ylsulfonyl)-α-D-galactopyranoside 在 sodium hydroxide 、 potassium tert-butylate 、 苄基三乙基氯化铵 作用下， 以 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 2.0h， 生成 (1S,3S,4R,5S,6S)-4,5-bis(benzyloxy)-1-[(benzyloxy)methyl]-7,7-dichloro-3-methoxy-2-oxabicyclo[4.1.0]heptane
  参考文献：
  名称：

  L-苏式-hex-4-enopyranosides的一些环丙烷化反应的立体过程

  摘要：

  完全保护的4-deoxy-α-L-苏-hex-4-enopyranosides 1c，d经过二氯卡宾加成，仅得到非对映异构体加成物5c，d，其环丙烷环抗C-3烷氧基取代基，而与3-未保护的衍生物1a，b提供了顺式和反式衍生物的混合物。在西蒙斯-史密斯环丙烷化加合物2a - d中获得具有顺式立体化学的化合物。从5b开始，环丙糖3b通过用LiAlH 4还原获得α ，β ，因此可以通过两个不同的途径立体选择地获得两个非对映异构体2b和3b。为了进行有用的比较，还对4-deoxy-β-L-苏-hex-4-enopyranoside 1e进行了上述两种环丙烷化方法，得到了预期的环加合物2e和二氯环加合物4e和5e的非对映异构体混合物（4e / 5e = 2.8 ：1）。

  DOI：

  10.1016/j.tet.2004.03.018
• 作为产物：
  描述：

  methyl 2,3,6-tri-O-benzyl-α-D-galactopyranoside 、 N,N-硫酰二咪唑 在 sodium hydride 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 3.0h， 以75%的产率得到methyl 2,3,6-tri-O-benzyl-4-O-(1H-imidazol-1-ylsulfonyl)-α-D-galactopyranoside
  参考文献：
  名称：

  An efficient and highly regioselective synthesis of 4-deoxy- and 2-acetamido-2,4-dideoxy-β-d-threo-hex-3-enopyranosides

  摘要：

  The preparation of the previously undescribed class of 4-deoxy- and 2,4-dideoxy-2-acetamido-beta-D-threo-hex-3-enopyranosides was accomplished with a very high yield and a complete regioselectivity by means of a simultaneous activation-elimination process of the OH-4 group of beta-D-talopyranosides (5a,b) and 2-acetamido-2-deoxy-beta-D-talopyranosides (5c,d) with NaH/'N,N'-sulfuryldiimidazole. The same reaction of analogous beta-D-galactopyranosides (5e,f) is not regioselective, leading to mixtures of 3- and 4-hexeno derivatives. This difference is evidently determined by the orientation of the C-2 substituent, which, in the talo series, is anti diaxially disposed to the H-3 eliminating group. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(02)00118-1

文献信息

• Steric course of some cyclopropanation reactions of L-threo-hex-4-enopyranosides
  作者：Antonino Corsaro、Ugo Chiacchio、Roberto Adamo、Venerando Pistarà、Antonio Rescifina、Roberto Romeo、Giorgio Catelani、Felicia D'Andrea、Manuela Mariani、Emanuele Attolino

  DOI：10.1016/j.tet.2004.03.018

  日期：2004.4

  Completely protected 4-deoxy-α-L-threo-hex-4-enopyranosides 1c,d undergo the dichlorocarbene addition affording exclusively diastereomeric adducts 5c,d with the cyclopropane ring anti to the C-3 alkyloxy substituent, while the reaction with 3-unprotected derivatives 1a,b affords a mixture of syn and anti derivatives. Under the Simmons–Smith cyclopropanation adducts 2a-d with a syn stereochemistry are

  完全保护的4-deoxy-α-L-苏-hex-4-enopyranosides 1c，d经过二氯卡宾加成，仅得到非对映异构体加成物5c，d，其环丙烷环抗C-3烷氧基取代基，而与3-未保护的衍生物1a，b提供了顺式和反式衍生物的混合物。在西蒙斯-史密斯环丙烷化加合物2a - d中获得具有顺式立体化学的化合物。从5b开始，环丙糖3b通过用LiAlH 4还原获得α ，β ，因此可以通过两个不同的途径立体选择地获得两个非对映异构体2b和3b。为了进行有用的比较，还对4-deoxy-β-L-苏-hex-4-enopyranoside 1e进行了上述两种环丙烷化方法，得到了预期的环加合物2e和二氯环加合物4e和5e的非对映异构体混合物（4e / 5e = 2.8 ：1）。
• An efficient and highly regioselective synthesis of 4-deoxy- and 2-acetamido-2,4-dideoxy-β-d-threo-hex-3-enopyranosides
  作者：Emanuele Attolino、Giorgio Catelani、Felicia D'Andrea

  DOI：10.1016/s0040-4039(02)00118-1

  日期：2002.2

  The preparation of the previously undescribed class of 4-deoxy- and 2,4-dideoxy-2-acetamido-beta-D-threo-hex-3-enopyranosides was accomplished with a very high yield and a complete regioselectivity by means of a simultaneous activation-elimination process of the OH-4 group of beta-D-talopyranosides (5a,b) and 2-acetamido-2-deoxy-beta-D-talopyranosides (5c,d) with NaH/'N,N'-sulfuryldiimidazole. The same reaction of analogous beta-D-galactopyranosides (5e,f) is not regioselective, leading to mixtures of 3- and 4-hexeno derivatives. This difference is evidently determined by the orientation of the C-2 substituent, which, in the talo series, is anti diaxially disposed to the H-3 eliminating group. (C) 2002 Elsevier Science Ltd. All rights reserved.