(2S,4aR,6R,7S,8R,8aS)-6-Allyl-7,8-bis-benzyloxy-2-phenyl-hexahydro-pyrano[3,2-d][1,3]dioxine | 592532-99-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (2S,4aR,6R,7S,8R,8aS)-6-Allyl-7,8-bis-benzyloxy-2-phenyl-hexahydro-pyrano[3,2-d][1,3]dioxine
• CAS: 592532-99-5
• 化学式: C₃₀H₃₂O₅
• 分子量: 472.581
• InChiKey: YQSPODVILTXYQP-FBLDLFPLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.61
• 重原子数：
  35.0
• 可旋转键数：
  9.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  46.15
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  (2S,4aR,6R,7S,8R,8aS)-6-Allyl-7,8-bis-benzyloxy-2-phenyl-hexahydro-pyrano[3,2-d][1,3]dioxine 在 sodium cyanoborohydride 、 臭氧 作用下， 以 四氢呋喃 、 吡啶 、 盐酸 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 7.0h， 生成 Thioacetic acid S-[(2R,3R,4R,5S,6R)-4,5-bis-benzyloxy-2-benzyloxymethyl-6-(2-oxo-ethyl)-tetrahydro-pyran-3-yl] ester
  参考文献：
  名称：

  Synthesis of thio-C-glycosides from 2′-carbonylalkyl C-glycosides by a tandem β-elimination and intramolecular hetero-Michael addition

  摘要：

  2'-Carbonyl 5-S-acetyl-C-glycofuranosides and 2'-carbonyl 4-S-acetyl-C-glycopyranosides were converted in good yields to respective 5-thio-C-glycopyranosides and 4-thio-C-glycofuranosides under base treatment. The transformation was resulted from beta-elimination on 2'-carbonyl C-glycoside to form alpha,beta-conjugated aldehyde (or ketone) and following intramolecular hetero-Michael addition by the thiol group. Crown Copyright (C) 2003 Published by Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(03)01039-6
• 作为产物：
  描述：

  allyl 2,3,4,6-tetra-O-acetyl-α-D-galactopyranoside 在 sodium methylate 、 sodium hydride 、 对甲苯磺酸 作用下， 以 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 2.0h， 生成 (2S,4aR,6R,7S,8R,8aS)-6-Allyl-7,8-bis-benzyloxy-2-phenyl-hexahydro-pyrano[3,2-d][1,3]dioxine
  参考文献：
  名称：

  Synthesis of thio-C-glycosides from 2′-carbonylalkyl C-glycosides by a tandem β-elimination and intramolecular hetero-Michael addition

  摘要：

  2'-Carbonyl 5-S-acetyl-C-glycofuranosides and 2'-carbonyl 4-S-acetyl-C-glycopyranosides were converted in good yields to respective 5-thio-C-glycopyranosides and 4-thio-C-glycofuranosides under base treatment. The transformation was resulted from beta-elimination on 2'-carbonyl C-glycoside to form alpha,beta-conjugated aldehyde (or ketone) and following intramolecular hetero-Michael addition by the thiol group. Crown Copyright (C) 2003 Published by Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(03)01039-6

文献信息

• Stereoselective synthesis of dioxabicycles from 1-<i>C</i>-allyl-2-<i>O</i>-benzyl-glycosides — An intramolecular cyclization between 2-<i>O</i>-benzyl oxygen and the allyl double bond
  作者：An-Tai Wu、Tian Yi、Huawu Shao、Shih-Hsiung Wu、Wei Zou

  DOI：10.1139/v06-046

  日期：2006.4.1

  Addition of a proton to the double bond of 1-C-allyl-O-benzylglycosides gave a 2′-carbonium ion, which in turn reacted intramolecularly, in a regio- and diastereo-selective manner, with the nucleophilic oxygen of the 2-O-benzyl group to form an oxonium intermediate. Subsequent cleavage of the benzyl C—O bond led to dioxabicycles in moderate yields. Surprisingly, opposite diastereoselectivities were observed from 1-C-allylglycofuranosides and 1-C-allylglycopyranosides, which produced 2,2′-trans- and 2,2′-cis-dioxabicycles, respectively.Key words: C-glycoside, olefin, cyclization, oxocarbonium, dioxabicycles.

  在 1-C-烯丙基-O-苄基糖苷的双键上加入一个质子会产生一个 2′-羰基离子，该离子又会以区域和非对映选择性的方式与 2-O-苄基的亲核氧发生分子内反应，形成一个羰基中间体。随后，苄基 CO 键裂解产生二恶英双环，产量适中。令人惊讶的是，1-C-烯丙基甘呋喃糖苷和 1-C-烯丙基甘吡喃糖苷的非对映选择性相反，它们分别生成 2,2′- 反式和 2,2′- 顺式二氧杂环：C-糖苷 烯烃 环化 氧化羰 二氧杂环
• Potent Neutralizing Antibodies Elicited by RBD-Fc-Based COVID-19 Vaccine Candidate Adjuvanted by the Th2-Skewing iNKT Cell Agonist
  作者：Xi-Feng Wang、Meng-Jia Zhang、Na He、Ya-Cong Wang、Cheng Yan、Xiang-Zhao Chen、Xiao-Fei Gao、Jun Guo、Rui Luo、Zheng Liu

  DOI：10.1021/acs.jmedchem.1c00881

  日期：2021.8.12