methyl 2,3,6-tri-O-benzyl-4-deoxy-α-L-threo-hex-4-enopyranoside | 161016-86-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: methyl 2,3,6-tri-O-benzyl-4-deoxy-α-L-threo-hex-4-enopyranoside
• 英文别名: (2R,3R,4S)-2-methoxy-3,4-bis(phenylmethoxy)-6-(phenylmethoxymethyl)-3,4-dihydro-2H-pyran
• CAS: 161016-86-0
• 化学式: C₂₈H₃₀O₅
• 分子量: 446.543
• InChiKey: ZCZXKAGJBIPGSI-UPRLRBBYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  33
• 可旋转键数：
  11
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  46.2
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  methyl 2,3,6-tri-O-benzyl-4-deoxy-α-L-threo-hex-4-enopyranoside 在 吡啶 、 镍 作用下， 以 四氢呋喃 为溶剂， 反应 117.0h， 生成 4-{methyl (5S)-2,3,6-tri-O-benzyl-4-deoxy-α-L-threo-hexopyranosid-5-O-yl}pentan-2-one
  参考文献：
  名称：

  Conformational evaluation of some 4-deoxyhex-4-enopyranose derivatives and their use in the preparation of a previously undescribed class of 3-thio-l-sorbopyranosides and their 6-C-methoxy analogues

  摘要：

  A new series of thio-substituted sugars were synthesised relying on the totally regio- and stereoselective cycloaddition of 4-deoxyhex-4-enopyranose derivatives to 'in situ' generated oxothiones. Conformational studies of the above unsaturated sugars showed a marked prevalence of the all-axial conformer. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0008-6215(02)00431-7
• 作为产物：
  描述：

  methyl 2,6-di-O-benzyl-β-D-galactopyranoside 在 sodium hydride 、 二正丁基氧化锡 、 N,N-硫酰二咪唑 作用下， 以 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 8.0h， 生成 methyl 2,3,6-tri-O-benzyl-4-deoxy-α-L-threo-hex-4-enopyranoside
  参考文献：
  名称：

  4-Deoxy-D-threo-hex-3-enopyranosides 的区域特异性合成通过同时激活——用 NaH/Im2SO2 系统消除 Talopyranoside 轴向 4-OH：立体电子效应的表现

  摘要：

  开发了一种用于区域选择性制备 4-deoxy- 和 2,4-dideoxy-2-acetamido-β-D-threo-hex-3-enopyranosides 的新的高产方法。该过程包括同时激活-消除 β-D-talopyranosides 和 2-acetamido-2-deoxy-β-D-talopyranosides 的 OH-4 基团，在 –30 时由 NaH/N,N'-sulfuryldiimidazole 系统介导℃。应用于类似的 β-D-吡喃半乳糖苷的相同反应在没有任何区域选择性的情况下发生，提供 hex-3- 和 hex-4-enopyranosides 的混合物。对于甲基 2,3,6-tri-O-benzyl-α-D-talo- 和 α-D-吡喃半乳糖苷，可以通过在 –30 °C 下淬灭反应来分离相应的 4-O-imidazylates . 将这些粗产物加热至室温后，α

  DOI：

  10.1002/ejoc.200600526

文献信息

• Synthesis of methyl 4-thio-β-cellobioside. A reinvestigation
  作者：Vincent Moreau、Jens Chr. Norrild、Hugues Driguez

  DOI：10.1016/s0008-6215(97)00046-3

  日期：1997.5

  Abstract The best yield for the synthesis of the title compound was obtained by nucleophilic displacement of the 4- O -triflyl group in methyl tri -O- benzyl -4-O- triflyl -β- d - galactopyranoside by 2,3,4,6- tetra -O- acetyl -1-S- acetyl-1-thio -β- d - glucopyranose in HMPA in the presence of diethylamine. Under these conditions, the formation of unsaturated side products was decreased.

  摘要通过亲核置换甲基三-O-苄基-4-O-三flyl-β-d-半乳糖吡喃糖苷中的4-O-三氟甲苯基，可得到2,3,4的最佳收率。在二乙胺存在下，HMPA中的6-四-O-乙酰基-1-S-乙酰基-1-硫代-β-d-吡喃葡萄糖。在这些条件下，减少了不饱和副产物的形成。
• 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）。
• A simple and highly diastereoselective preparation of glycal epoxides using the MCPBA-KF complex
  作者：Giuseppe Bellucci、Giorgio Catelani、Cinzia Chiappe、Felicia D'Andrea

  DOI：10.1016/s0040-4039(00)74426-1

  日期：1994.11

  Glycols ore converted to the corresponding epoxides in high yields by a diastereoselective one-step epoxidation using the m-chloroperoxybenzoic acid-KF complex in anhydrous dichloromethane.
• A new route to d-xylo-hexos-5-ulose and some of its selectively protected derivatives from d-galactose
  作者：Pier Lugi Barili、Giancarlo Berti、Giorgio Catelani、Felicia D'Andrea、Francesco De Rensis

  DOI：10.1016/s0040-4020(97)00536-x

  日期：1997.6

  A new approach to D-xylo-hexos-5-ulose, a useful synthetic intermediate, is described, starting from methyl beta-D-galactopyranoside and involving as the key step an epoxidation/methanolysis of 3-O-protected methyl 2,6-di-O-benzyl-4-deoxy-alpha-L-threo-hex-4-enopyranosides, to produce bis-glycosides of the parent dicarbonylic sugar, which can be obtained free or selectively protected through hydrogenolytic and/or hydrolytic procedures. The diastereo- and regioselectivity of the epoxidation and solvolysis steps are investigated and tentatively interpreted, and new products characterized by NMR techniques, (C) 1997 Elsevier Science Ltd.
• 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.