(2R,3S,4R,6R)-4-(benzyloxy)-2-methyl-6-(phenylthio)tetrahydro-2H-pyran-3-yl trifluoromethanesulfonate | 1561048-49-4

• 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: (2R,3S,4R,6R)-4-(benzyloxy)-2-methyl-6-(phenylthio)tetrahydro-2H-pyran-3-yl trifluoromethanesulfonate
• CAS: 1561048-49-4
• 化学式: C₂₀H₂₁F₃O₅S₂
• 分子量: 462.511
• InChiKey: KKHJBMARTHOMLJ-AXUOBQJMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.73
• 重原子数：
  30.0
• 可旋转键数：
  7.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  61.83
• 氢给体数：
  0.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  、 (2R,3S,4R,6R)-4-(benzyloxy)-2-methyl-6-(phenylthio)tetrahydro-2H-pyran-3-yl trifluoromethanesulfonate 在 sodium hydride 、 15-冠醚-5 作用下， 以 1,4-二氧六环 、 mineral oil 为溶剂， 反应 24.17h， 以59%的产率得到
  参考文献：
  名称：

  Direct Synthesis of 2-Deoxy-β-Glycosides via Anomeric O-Alkylation with Secondary Electrophiles

  摘要：

  An approach for direct synthesis of biologically significant 2-deoxy-beta-glycosides has been developed via O-alkylation of a variety of 2-deoxy-sugar-derived anomeric alkoxides using challenging secondary triflates as electrophiles. It was found a free hydroxyl group at C3 of the 2-deoxy-sugar-derived lactols is required in order to achieve synthetically efficient yields. This method has also been applied to the convergent synthesis of a 2-deoxy-beta-tetrasaccharide.

  DOI：

  10.1021/ja4116956
• 作为产物：
  描述：

  6-deoxy-D-glucal 在 吡啶 、 ReOCl₃(SMe₂)(OPPh₃) 、 二正丁基氧化锡 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 3.5h， 生成 (2R,3S,4R,6R)-4-(benzyloxy)-2-methyl-6-(phenylthio)tetrahydro-2H-pyran-3-yl trifluoromethanesulfonate
  参考文献：
  名称：

  Direct Synthesis of 2-Deoxy-β-Glycosides via Anomeric O-Alkylation with Secondary Electrophiles

  摘要：

  An approach for direct synthesis of biologically significant 2-deoxy-beta-glycosides has been developed via O-alkylation of a variety of 2-deoxy-sugar-derived anomeric alkoxides using challenging secondary triflates as electrophiles. It was found a free hydroxyl group at C3 of the 2-deoxy-sugar-derived lactols is required in order to achieve synthetically efficient yields. This method has also been applied to the convergent synthesis of a 2-deoxy-beta-tetrasaccharide.

  DOI：

  10.1021/ja4116956

文献信息

• Stereoselective Construction of β‐Mannopyranosides by Anomeric <i>O</i> ‐Alkylation: Synthesis of the Trisaccharide Core of <i>N</i> ‐linked Glycans
  作者：Hai Nguyen、Danyang Zhu、Xiaohua Li、Jianglong Zhu

  DOI：10.1002/anie.201600488

  日期：2016.4.4

  for direct and stereoselective synthesis of β‐mannopyranosides by anomeric O‐alkylation has been developed. This anomeric O‐alkylation of mannopyranose‐derived lactols is proposed to occur under synergistic control of a kinetic anomeric effect and metal chelation. The presence of a conformationally flexible C6 oxygen atom in the sugar‐derived lactol donors is required for this anomeric O‐alkylation to

  开发了一种通过异头O-烷基化直接和立体选择性合成β-甘露聚糖的新方法。甘露聚糖吡喃糖衍生的乳糖醇的这种异头O-烷基化被提议在动力学异头作用和金属螯合的协同控制下发生。为了使这种端基异构O-烷基化有效，需要糖衍生的乳糖醇供体中存在构象柔性的C6氧原子，这可能是由于其与铯离子的螯合。相反，C 2氧原子的存在起着较小的作用。这种糖基化方法已成功用于合成复杂的N-连接聚糖的三糖核心。
• Stereoselective Synthesis of α-Digitoxosides and α-Boivinosides via Chelation-Controlled Anomeric<i>O</i>-Alkylation
  作者：Danyang Zhu、Surya Adhikari、Kedar N. Baryal、Belal N. Abdullah、Jianglong Zhu

  DOI：10.1080/07328303.2014.931965

  日期：2014.10.13

  A chelation-controlled anomeric O-alkylation has been developed for the stereoselective synthesis of α-digitoxosides and α-boivinosides bearing a C3-free hydroxyl group. Due to chelation via sodium ion, the anomeric alkoxides are locked in the axial configuration, which leads to the selective production of α-glycosides.

  已经开发了螯合控制的异头O-烷基化反应，用于立体选择性地合成α-数字氧苷和带有C3-游离羟基的α-boivinosides。由于经由钠离子的螯合，异头醇盐被锁定在轴向构型中，这导致选择性产生α-糖苷。
• Synthesis of the 2-deoxy trisaccharide glycal of antitumor antibiotics landomycins A and E
  作者：Xiaohua Li、Justin Woodward、Ali Hourani、Danyang Zhu、Sabrine Ayoub、Jianglong Zhu

  DOI：10.1016/j.carres.2016.04.031

  日期：2016.7

  Synthesis of the 2-deoxy trisaccharide glycal of antitumor antibiotics landomycins A and E has been described. The synthesis involves an anomeric O-alkylation for the synthesis of 2-deoxy beta-linked disaccharide, a tert-butyldimethylsilyl triflate-catalyzed alpha-selective L-rhodinosylation, and a lithium 4,4'-di-tert-butylbiphenyl-mediated reductive debenzylation and concomitant reductive lithiation-elimination

  已经描述了抗肿瘤抗生素兰霉素A和E的2-脱氧三糖糖基的合成。该合成涉及用于合成2-脱氧β-连接的二糖的异头O-烷基化，叔丁基二氟甲磺酸叔丁基二甲基甲硅烷基催化的α-选择性L-古丁糖基化和4,4'-二叔丁基联苯锂介导的还原反应脱苄基化和伴随的还原性锂化消除，以生产2-脱氧三糖。
• Synthesis of 2-Amino-2-deoxy-β-<scp>d</scp>-mannosides via Stereoselective Anomeric <i>O</i>-Alkylation of 2<i>N</i>,3<i>O</i>-Oxazolidinone-Protected <scp>d</scp>-Mannosamine: Synthesis of the Trisaccharide Repeating Unit of <i>Streptococcus pneumoniae</i> 19F Polysaccharide
  作者：Bishwa Raj Bhetuwal、Fenglang Wu、Padam Prasad Acharya、Prakash Thapa、Jianglong Zhu

  DOI：10.1021/acs.orglett.3c01564

  日期：2023.6.9

  Cesium carbonate-mediated stereoselective anomeric O-alkylation of a 2N,3O-oxazolidinone-protected d-mannosamine with sugar-derived primary or secondary alkyl triflates afforded the corresponding 2-amino-2-deoxy-β-d-mannosides in moderate to good yields and excellent stereoselectivity. The oxazolidinone ring can be opened with aqueous alkali hydroxide to liberate the amine functionality. This method

  碳酸铯介导的 2 N ,3 O-恶唑烷酮保护的d-甘露糖胺与糖衍生的伯或仲烷基三氟甲磺酸酯的立体选择性异头O-烷基化，以中等程度提供相应的 2-氨基-2-脱氧-β- d-甘露糖苷。以获得良好的产率和优异的立体选择性。恶唑烷酮环可以用碱金属氢氧化物水溶液打开以释放胺官能团。该方法已成功应用于肺炎链球菌19F多糖三糖重复单元的合成。