2,3,4-三-氧-苄基-D-吡喃核糖 | 20787-21-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 2,3,4-三-氧-苄基-D-吡喃核糖
• 英文名称: 2,3,4-tri-O-benzyl-D-ribopyranose
• 英文别名: (3R,4R,5R)-3,4,5-tris(Benzyloxy)tetrahydro-2H-pyran-2-ol；(3R,4R,5R)-3,4,5-tris(phenylmethoxy)oxan-2-ol
• CAS: 20787-21-7
• 化学式: C₂₆H₂₈O₅
• 分子量: 420.505
• InChiKey: HTSKDJMXBBFKKG-NITSXXPLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  31
• 可旋转键数：
  9
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  57.2
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  2,3,4-三-氧-苄基-D-吡喃核糖 在 palladium dihydroxide 氯化亚砜 、 氢气 、 四丁基碘化铵 、 双(三甲基硅烷基)氨基钾 、 sodium hydride 、 magnesium 、 二甲基亚砜 、 三乙胺 作用下， 以 四氢呋喃 、 乙醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 52.0h， 生成 (5S,6R,7S,8S)-Undecane-1,5,6,7,8-pentaol
  参考文献：
  名称：

  Universal NMR Databases for Contiguous Polyols

  摘要：

  On the basis of 1,2,3-triols 1asimilar tod, 1,2,3,4-tetraols 2asimilar toh, and 1,2,3,4,5-pentaols 3asimilar top, NMR databases with four types of profile-descriptors (C-13-, H-1-, and H-1(OH)-chemical shifts and vicinal spin-coupling constants) for contiguous polyols are reported. To systematically assess the relative values of these databases, a case study has been conducted on heptaols 4asimilar tod, through which the gamma- and delta-effects have been recognized to refine the C-13 and H-1 chemical shift profile predicted via an application of the concept of self-contained nature. The magnitudes of gamma- and delta-effects depend on a specific stereochemical arrangement of the functional groups present in both the inside and outside of a self-contained box and are significant only for the stereoisomers belonging to a specific sub-group. With the exception of the stereochemical arrangement of functional groups belonging to a specific sub-group, the gamma- and delta-effects can, at the first order of approximation, be ignored for the stereochemical analysis of unknown compounds. For the stereoisomers belonging to a specific sub-group, it is necessary to refine, with incorporation of the gamma- and delta-effects, the profile predicted at the first order of approximation. With use of heptaols 4asimilar tod, the values of (3)J(H,H) profiles have been assessed. Two methods, one using profiles consisting of three contiguous (3)J(H,H) constants and the other using profiles consisting of two contiguous (3)J(H,H) constants, have been developed. A stereochemical analysis based on three, or two, contiguous (3)J(H,H) profiles is operationally simpler than one based on C-13 and H-1 chemical shift profiles. Therefore, it is recommended to use a (3)J(H,H) profile as the primary device to predict the stereochemistry of unknown polyols and C-13 and H-1 chemical shift profiles as the secondary devices to confirm the predicted stereochemistry.

  DOI：

  10.1021/ja0375481
• 作为产物：
  描述：

  1-甲基-2,3,4-三-氧-苄基Β-D-吡喃核糖 在 硫酸 、 溶剂黄146 作用下， 反应 2.0h， 以31%的产率得到2,3,4-三-氧-苄基-D-吡喃核糖
  参考文献：
  名称：

  吡喃糖的立体选择性C-糖基化反应：甘露糖基阳离子的构象偏好和反应

  摘要：

  进行了与甘露糖和其他吡喃糖酶有关的缩醛的C-糖基化的系统研究。C-5烷氧基烷基仅对立体选择性提供适度的影响。另一方面，对在C-2，C-3和C-4处带有烷氧基的戊基吡喃糖的研究表明，烷氧基对选择性有重要影响。甘露糖的情况下，与观察到的高选择性α Ç -mannosylation反向以高选择性β如果C-5的烷氧基烷基中除去。对中间氧碳鎓离子（包括甘露糖基阳离子）的构象偏爱的分析，以及对亲核进攻过渡态中产生的空间效应的考虑，为这些现象提供了解释。

  DOI：

  10.1021/jo0522963

文献信息

• Divergent total synthesis of d-ribo-phytosphingosine and l-ribo-phytosphingosine from d-ribose
  作者：Jong Soo Chun、Seung Min Hong、Tae Hong Jeon、Sook Jin Park、Han Pyo Son、Jun Min Jung、Young Jae Choi、In Su Kim、Young Hoon Jung

  DOI：10.1016/j.tet.2016.11.018

  日期：2016.12

  Divergent total synthesis of d-ribo-phytosphingosine (1) and l-ribo-phytosphingosine (2) was achieved from readily available d-ribose via cross-metathesis reaction, Wittig reaction, and diastereoselective amination reaction of allylic ethers using chlorosulfonyl isocyanate (CSI) as the key steps. As results, reactions of anti-1,2-dibenzyl ethers 11 and 16 with chlorosulfonyl isocyanate afforded exclusively

  的发散总合成d -核糖-phytosphingosine（1）和升-核糖-phytosphingosine（2）从容易获得的取得d -核糖通过交叉复分解反应，Wittig反应，并用磺酰异氰酸酯的烯丙基醚的非对映选择性的氨基化反应（CSI ）作为关键步骤。结果，抗-1,2-二苄基醚11和16与氯磺酰基异氰酸酯反应，仅得到抗-1,2-氨基醇12和17。非对映选择性为32：1和31：1，产率分别为75％和76％。这些结果可以通过邻近基团效应来解释，从而导致立体化学的保留。
• A Practical Synthesis of Sugar-Derived Cyclic Nitrones: Powerful Synthons for the Synthesis of Iminosugars
  作者：Yue-Mei Jia、Chu-Yi Yu、Wu-Bao Wang、Mu-Hua Huang、Yi-Xian Li、Pei-Xin Rui、Xiang-Guo Hu、Wei Zhang、Jia-Kun Su、Zhao-Lan Zhang、Jian-She Zhu、Wei-Hua Xu、Xian-Qing Xie

  DOI：10.1055/s-0029-1219189

  日期：2010.2

  Sugar-derived cyclic nitrones were synthesized from the corresponding aldoses through an efficient and practical procedure involving a seven-step reaction sequence in good to excellent overall yield (10-42%). This synthetic strategy, requiring only inexpensive reagents, is easy to perform and hence suitable for large-scale preparations.

  从相应的醛糖通过一种高效实用的过程合成了糖源性环硝酮，该过程涉及七个步骤反应，整体产率为良好到优秀（10-42%）。这种合成策略只需使用廉价试剂，操作简单，因此适合大规模制备。
• Straightforward Synthesis of Diverse 1-Deoxyazapyranosides via Stereocontrolled Nucleophilic Additions to Six-Membered Cyclic Nitrones
  作者：Ting-Hao Chan、Yi-Fan Chang、Jung-Jung Hsu、Wei-Chieh Cheng

  DOI：10.1002/ejoc.201001045

  日期：2010.10

  A systematic study of diastereoselective nucleophilic addition of Grignard reagents to six-membered chiral tri-O-benzyl cyclic nitrones is described. With all eight chiral cyclic nitrones and asymmetric reaction conditions in hand, a practical methodology is established for the preparation of diverse 1-deoxyazapyranosides bearing various stereogenic centers.

  描述了格氏试剂对六元手性三-O-苄基环硝酮的非对映选择性亲核加成的系统研究。掌握了所有八种手性环状硝酮和不对称反应条件，建立了一种实用的方法来制备带有各种立体中心的各种 1-脱氧氮杂吡喃糖苷。
• Regioselective and Diastereoselective Amination of Polybenzyl Ethers Using Chlorosulfonyl Isocyanate:  Total Syntheses of 1,4-Dideoxy-1,4-imino-<scp>d</scp>-arabinitol and (−)-Lentiginosine
  作者：In Su Kim、Ok Pyo Zee、Young Hoon Jung

  DOI：10.1021/ol061614x

  日期：2006.8.1

  The total syntheses of DAB1 (1) and (-)-lentiginosine (2) were concisely accomplished from D-lyxose via regioselective and diastereoselective NHCbz introduction using CSI, chemoselective removal of the Cbz protection, and ring-closing metathesis as key steps.

  通过使用CSI的区域选择性和非对映选择性NHCbz导入，化学选择性去除Cbz保护和闭环易位作为关键步骤，由D-lyxose精确地完成了DAB1（1）和（-）-lentiginosine（2）的总合成。
• Application of a tandem seleno-michael/aldol reaction in the total syntheses of (+)-Pericosine B, (+)-Pericosine C, (+)-COTC and 7-chloro-analogue of (+)-Gabosine C
  作者：Natalia Biduś、Piotr Banachowicz、Szymon Buda

  DOI：10.1016/j.tet.2020.131397

  日期：2020.8

  Synthesis of (+)-Pericosine B, (+)-Pericosine C, (+)-COTC and a 7-chloro-analogue of (+)-Gabosine C was achieved via tandem seleno-Michael/aldol reactions as key steps. The carbasugar linear precursor was obtained from cheap and readily available d-ribose in 7 steps which included resolution of the d-ribopyranose and the d-ribofuranose forms. Further transformation of the cyclic product involving a

  （+）-Pericosine B，（+）-Pericosine C，（+）-COTC和（+）-Gabosine C的7-氯类似物的合成是通过串联硒代-Michael / aldol反应作为关键步骤实现的。Carbasugar线性前体可通过7个步骤从廉价且容易获得的d-核糖中获得，包括拆分d-核糖吡喃糖和d-核呋喃糖形式。涉及区域选择性Steglich酯化或仲羟基甲基化的环状产物的进一步转化产生了受保护的（+）-COTC，（+）-Pericosine B和（+）-PericosineC。苄基醚在-78°脱保护C以令人满意的产率得到标题化合物。