3,4,6-tri-O-benzyl-1,2-dideoxy-1β-(prop-2-enyl)-D-arabino-hexopyranose | 129778-39-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3,4,6-tri-O-benzyl-1,2-dideoxy-1β-(prop-2-enyl)-D-arabino-hexopyranose
• 英文别名: 1-allyl-1,2-dideoxy-3,4,6-tri-O-benzyl-D-glucopyranose；3-(3,4,6-tri-O-benzyl-2-deoxy-β-D-glucopyranosyl)-1-propene；(2R,3S,4R,6S)-3,4-bis(phenylmethoxy)-2-(phenylmethoxymethyl)-6-prop-2-enyloxane
• CAS: 129778-39-8
• 化学式: C₃₀H₃₄O₄
• 分子量: 458.598
• InChiKey: SJPLLCXSCOAHKE-KJHMZRPRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.6
• 重原子数：
  34
• 可旋转键数：
  12
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  36.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  phenyl 3,4,6-tri-O-benzyl-2-deoxy-1-sulphonyl-αβ-D-arabino-pyranoside 在 氢氧化钾 作用下， 生成 3,4,6-tri-O-benzyl-1,2-dideoxy-1β-(prop-2-enyl)-D-arabino-hexopyranose
  参考文献：
  名称：

  Synthesis of 2-deoxy-β-C-pyranosides by diastereoselective hydrogen atom transfer

  摘要：

  DOI：

  10.1016/s0040-4039(00)98814-2

文献信息

• <i>C</i>-Glycosylation enabled by <i>N</i>-(glycosyloxy)acetamides
  作者：Miao Liu、Bo-Han Li、Tian Li、Xia Wu、Meng Liu、De-Cai Xiong、Xin-Shan Ye

  DOI：10.1039/d0ob00561d

  日期：——

  The C-glycosylation of C-nucleophiles including allyltrimethylsilane, silyl enol ethers and phenols with N-(glycosyloxy)acetamides as glycosyl donors has been realized. This protocol provides a convenient and practical route for the synthesis of alkyl C-glycosides and aryl 2-deoxy-β-C-glycosides under mild reaction conditions.

  已经实现了包含N-（糖基氧基）乙酰胺作为糖基供体的C-亲核试剂（包括烯丙基三甲基硅烷，甲硅烷基烯醇醚和苯酚）的C-糖基化。该方案为在温和的反应条件下合成烷基C-糖苷和芳基2-脱氧-β-C-糖苷提供了方便实用的途径。
• Gold(<scp>i</scp>)-catalyzed C-glycosylation of glycosyl ortho-alkynylbenzoates: the role of the moisture sequestered by molecular sieves
  作者：Xiaoping Chen、Qiaoling Wang、Biao Yu

  DOI：10.1039/c6cc07218f

  日期：——

  C-Glycosylation of glycosyl ortho-hexynylbenzoates with allyltrimethylsilane or silyl enol ethers could proceed smoothly under the catalysis of Ph₃PAuNTf₂, wherein the moisture sequestered by the molecular sieves ensured the gold(i)-catalytic cycle.

  将glycosyl ortho-hexynylbenzoates与allyltrimethylsilane或硅烯醚进行C-糖基化反应，可在Ph3PAuNTf2的催化下顺利进行，其中分子筛吸附的水分确保了金（i）催化循环的进行。
• The Effect of Electrostatic Interactions on Conformational Equilibria of Multiply Substituted Tetrahydropyran Oxocarbenium Ions
  作者：Michael T. Yang、K. A. Woerpel

  DOI：10.1021/jo8017846

  日期：2009.1.16

  the conformational preference of the C-5 alkoxymethyl group. Although the monosubstituted C-5 alkoxymethyl substituent preferred a pseudoequatorial orientation, the C-5−C-6 bond rotation was controlled by an electrostatic effect. The preferred diaxial conformer of the trans-4,5-disubstituted tetrahydropyranyl system underscored the importance of electrostatic effects in dictating conformational equilibria

  通过对光谱、计算和反应性数据的分析，确定了与糖基阳离子相关的二氧碳鎓离子的三维结构。二氧碳鎓离子的假设低能量结构与实验确定的两者相关1H NMR 耦合常数和非对映选择性来自亲核取代反应。该方法证实了 C-3 烷氧基取代系统的假轴偏好，并揭示了 C-5 烷氧基甲基的构象偏好。尽管单取代的 C-5 烷氧基甲基取代基优选伪赤道取向，但 C-5-C-6 键旋转受静电效应控制。反式-4,5-二取代四氢吡喃系统的首选双轴构象异构体强调了静电效应在决定构象平衡方面的重要性。在 2-脱氧甘露糖体系中，虽然空间效应影响 C-5 烷氧基甲基取代基的取向，但由于静电稳定，全轴构象异构体受到青睐。
• Reduction of 2-Arylthio-<font>β</font>-<i>C</i>-<scp>D</scp>-Glucopyranosides with Different Functional Groups in the Lateral Chain
  作者：Mingming Han、Irina P. Smoliakova

  DOI：10.1080/00397911.2010.481738

  日期：2011.3.28

  [image omitted] 2-Arylthio--C-D-glucopyranosides with a carbonyl or methoxy group in the lateral chain (1 and 2) can be converted to the corresponding 2-deoxy--C-D-glucopyranosides (1a and 2a) using Raney Ni. Reduction of 2-arylthio--C-D-glucopyranosides bearing an ester, methoxy, CN, or C=C moiety in the side chain (3-6) using n-Bu3SnH in the presence of azobisisobutyronitrile (AIBN) provided the corresponding 2-deoxy--C-D-glucopyranosides (3a-6a) without reducing additional functional groups. The application of n-Bu3SnH and AIBN in reaction with 2-arylthio--C-D-glucopyranoside (7) containing a Me3Si group bonded to the carbonyl fragment (7) resulted in the reduction of both the 2-ArS and C=O groups.
• Erosion of Stereochemical Control with Increasing Nucleophilicity: <i>O</i>-Glycosylation at the Diffusion Limit
  作者：Matthew G. Beaver、K. A. Woerpel

  DOI：10.1021/jo902222a

  日期：2010.2.19

  Nucleophilic substitution reactions of 2-deoxyglycosyl donors indicated that the reactivity of the oxygen nucleophile has a significant impact on stereoselectivity. Employing ethanol as the nucleophile resulted in a 1:1 (alpha:beta) ratio of diastereomers under S(N)1-like reaction conditions. Stercoselective formation of the 2-deoxy-alpha-O-glycoside was only observed when weaker nucleophiles, such as trifluoroethanol, were employed. The lack of stercoselectivity observed in reactions of common oxygen nucleophiles can be attributed to reaction rates of the stereochemistry-determining step that approach the diffusion limit. In this scenario, both faces of the prochiral oxocarbenium ion are subject to nucleophilic addition to afford a statistical mixture of diastercomeric products. Control experiments confirmed that all nucleophilic substitution reactions were performed under kinetic control.