2,3,4-tri-O-benzyl-D-arabinopyranose | 18039-26-4

• 物质功能分类: 生物化工 - 糖类化合物 - 单糖
• 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: 2,3,4-tri-O-benzyl-D-arabinopyranose
• 英文别名: 2,3,4-tri-O-benzyl-D-arabinose；tri-2,3,4-O-benzyl-D-arabinose；tribenzyl-D-arabinose；(3S,4R,5R)-3,4,5-Tris(benzyloxy)tetrahydro-2H-pyran-2-ol；(3S,4R,5R)-3,4,5-tris(phenylmethoxy)oxan-2-ol
• CAS: 18039-26-4；20787-16-0；20787-21-7；77943-32-9；77943-33-0；89615-43-0；89615-44-1；90899-55-1
• 化学式: C₂₆H₂₈O₅
• 分子量: 420.505
• InChiKey: HTSKDJMXBBFKKG-DYXQDRAXSA-N

物化性质

• 熔点：
  67-70°C
• 沸点：
  566.0±50.0 °C(Predicted)
• 密度：
  1.21±0.1 g/cm3(Predicted)

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

安全信息

• 安全说明：
  S22,S24/25

反应信息

• 作为反应物：
  描述：

  2,3,4-tri-O-benzyl-D-arabinopyranose 在 palladium dihydroxide 、 palladium on activated charcoal 咪唑 、 盐酸 、 sodium tetrahydroborate 、 四氧化锇 、 迭氮酸 、 草酰氯 、 氢气 、 双(三甲基硅烷基)氨基钾 、 potassium carbonate 、 sodium hydrogensulfite 、 二甲基亚砜 、 N-甲基吗啉氧化物 、 三乙胺 、 三苯基膦 、 偶氮二甲酸二乙酯 作用下， 以 四氢呋喃 、 甲醇 、 乙醇 、 乙酸乙酯 、 N,N-二甲基甲酰胺 、 苯 为溶剂， 反应 153.84h， 生成 (1R,2R,3R,9R,9aR)-1,2,3,9-tetrahydroxyquinolizidine
  参考文献：
  名称：

  Synthesis of Tetrahydroxyquinolizidines:  Ring-Expanded Analogs of the Mannosidase Inhibitor Swainsonine

  摘要：

  The indolizidine azasugar swainsonine (1) is an important inhibitor of mannosidase II and has shown antitumor and immunomodulatory activity. A comparison of the structure of swainsonine and D-mannopyranose shows that swainsonine lacks the C(4) hydroxymethine group of mannose. Ring-expanded quinolizidine analogs 4 of swainsonine were prepared where the ''missing'' hydroxymethine group was incorporated into the pyrrolidine ring of swainsonine between C(1) and C(8a). The quinolizidine analogs 4 resemble both D-mannopyranose and the related azasugar deoxymannojirimycin, a selective inhibitor of the glycoprotein processing enzyme mannosidase I. D-Arabinose was converted into the omega-halo azidoalkene 13, which was subjected to thermolysis, a strategy which had been successful in an earlier synthesis of swainsonine itself. Rather than the desired quinolizidine 4, the pyridinium ion 16 was produced. An alternate synthesis of all four C(9)/C(9a) diastereomers of 4 was developed which relied on the reductive double-alkylation of epoxides bearing remote azido and chloro groups. Thus, reduction of compounds 21 alpha, 21 beta, 26, and 27 resulted in the formation of the quinolizidines 22, 23, 28, and 29, which were deprotected to give the quinolizidine analogs of swainsonine (9S,9aR)-4, (9R,9aS)-4, (9S,9aS)-4, and (9R,9aR)-4, respectively. An alternate synthesis of(9R,9aR)-4 involving the reductive N-alkylation of a cyclic imine was also developed. None of the quinolizidines showed significant glycosidase activity in screens against mannosidases, glucosidases, or fucosidases. Speculation on the significance of these findings is presented.

  DOI：

  10.1021/jo960609b
• 作为产物：
  描述：

  methyl D-arabinopyranoside 在 硫酸 、 sodium hydride 、 溶剂黄146 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 2.0h， 生成 2,3,4-tri-O-benzyl-D-arabinopyranose
  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

• Synthesis of Polyhydroxylated Quinolizidine and Indolizidine Scaffolds from Sugar-Derived Lactams via a One-Pot Reduction/Mannich/Michael Sequence
  作者：Piotr Szcześniak、Sebastian Stecko、Elżbieta Maziarz、Olga Staszewska-Krajewska、Bartłomiej Furman

  DOI：10.1021/jo502146z

  日期：2014.11.7

  A direct approach to the synthesis of indolizidine and quinolizidine scaffolds of iminosugars is described. The presented strategy is based on a one-pot sugar lactam reduction with Schwartz’s reagent followed by a diastereoselective Mannich/Michael tandem reaction of the resulting sugar imine with Danishefsky’s diene. The stereochemical course of the investigated reaction has been explained in detail

  描述了一种直接合成亚氨基糖的吲哚并立定和喹喔嗪骨架的方法。提出的策略是基于先用Schwartz试剂还原一锅糖内酰胺，然后再将得到的糖亚胺与Danishefsky的二烯进行非对映选择性的Mannich / Michael串联反应。已详细解释了所研究反应的立体化学过程。所获得的双环产物是用于合成各种天然存在的多羟基化生物碱及其衍生物的有吸引力的结构单元。
• 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。
• One-carbon extrusion from carbohydrates via C1-alkoxy radical fragmentation. An easy access to erythrose and threose
  作者：Junji Inanaga、Yuichi Sugimoto、Yasuo Yokoyama、Takeshi Hanamoto

  DOI：10.1016/s0040-4039(00)74732-0

  日期：1992.12

  Generation and fragmentation of the C1-alkoxy radicals of pyranose derivatives are nicely promoted by (diacetoxyiodo)benzene or lead tetraacetate in the presence of iodine catalyst under mild conditions to give the corresponding mixed-acetal formates which are further converted to the furanose derivatives by acid-catalysed transacetalization.

  在温和的条件下，在碘催化剂的存在下，（二乙酰氧基碘）苯或四乙酸铅很好地促进了吡喃糖衍生物的C1-烷氧基的生成和断裂，从而生成了相应的混合缩醛甲酸酯，并通过酸将其进一步转化为呋喃糖衍生物。 -催化的缩醛化。
• 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。