p-tolyl 6-O-(tert-butyldimethylsilyl)-1-thio-β-D-glucopyranoside | 794520-99-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: p-tolyl 6-O-(tert-butyldimethylsilyl)-1-thio-β-D-glucopyranoside
• CAS: 794520-99-3
• 化学式: C₁₉H₃₂O₅SSi
• 分子量: 400.612
• InChiKey: CQMYMLZUQKZDNG-SFFUCWETSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.92
• 重原子数：
  26.0
• 可旋转键数：
  5.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.68
• 拓扑面积：
  79.15
• 氢给体数：
  3.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  p-tolyl 6-O-(tert-butyldimethylsilyl)-1-thio-β-D-glucopyranoside 在 吡啶 、 4-二甲氨基吡啶 、 DMTST 作用下， 以 二氯甲烷 为溶剂， 反应 5.5h， 生成 [(3aR,5R,6R,7S,7aR)-7-acetyloxy-2-[(3R)-3-acetyloxypent-4-ynoxy]-5-[[tert-butyl(dimethyl)silyl]oxymethyl]-2-methyl-5,6,7,7a-tetrahydro-3aH-[1,3]dioxolo[4,5-b]pyran-6-yl] acetate
  参考文献：
  名称：

  Total synthesis of bidensyneosides A2 and C: remarkable protecting group effects in glycosylation

  摘要：

  Bidensyneosides are a group of five recently identified polyacetylenic glucosides from Bidens parviflora WILLD, a traditional Chinese medicinal plant that contains rich bioactive natural products. It was shown that bidensyneosides inhibited both histamine release and nitric oxide production. The synthesis of bidensyneoside A2 (2) and C (4) as well as 3-deoxybidensyneoside C (5) are described. These syntheses establish a synthetic entry to the bidensyneosides and confirm the stereochemistry at C3. Furthermore, a remarkable protecting Group effect on orthoester formation was observed during the glycosylation reaction. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2004.08.012
• 作为产物：
  描述：

  p-tolyl-2,3,4,6-tetra-O-acetyl-1-thio-β-D-glucopyranoside 在 咪唑 、 potassium carbonate 作用下， 以 甲醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 3.5h， 生成 p-tolyl 6-O-(tert-butyldimethylsilyl)-1-thio-β-D-glucopyranoside
  参考文献：
  名称：

  Total synthesis of bidensyneosides A2 and C: remarkable protecting group effects in glycosylation

  摘要：

  Bidensyneosides are a group of five recently identified polyacetylenic glucosides from Bidens parviflora WILLD, a traditional Chinese medicinal plant that contains rich bioactive natural products. It was shown that bidensyneosides inhibited both histamine release and nitric oxide production. The synthesis of bidensyneoside A2 (2) and C (4) as well as 3-deoxybidensyneoside C (5) are described. These syntheses establish a synthetic entry to the bidensyneosides and confirm the stereochemistry at C3. Furthermore, a remarkable protecting Group effect on orthoester formation was observed during the glycosylation reaction. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2004.08.012

文献信息

• From organocatalysed desilylations to high-yielding benzylidenations of electron-deficient benzaldehydes
  作者：Qun Niu、Linlin Xing、Chunbao Li

  DOI：10.3184/174751917x14955339414758

  日期：2017.6

  A new type of organoprecatalyst (MeSCH2Cl/KI) for desilylation and benzylidenation reactions has been designed. Both reactions are user friendly and high yielding (71–>99%) and have fast reaction rates. The desilylation of iodo silyl ethers was achieved with no sequential etherification side reactions like those seen for reactions when using TBAF. In the application of the catalytic system to a 6-TBDMS

  设计了一种用于脱甲硅烷基化和亚苄基化反应的新型有机预催化剂（MeSCH2Cl/KI）。两种反应都对用户友好且产率高 (71–>99%)，并且反应速度快。碘甲硅烷基醚的脱甲硅烷基化是在没有像使用 TBAF 的反应中看到的那样的连续醚化副反应实现的。在将催化系统应用于葡萄糖苷的 6-TBDMS 醚时，使用缺电子苯甲醛的葡萄糖苷苄基化以 87% 的产率实现，而先前报道的产率为 69-77%。总共使用甲硅烷氧基醇和缺电子苯甲醛代替它们的活化缩醛形式实现了 14 次苯亚甲基化反应。在反应速率和产率方面，苯亚甲基化的顺序是对氟苯甲醛>苯甲醛> 对茴香醛，并讨论了可能的机制。这些实验初步将这种具有成本效益的催化系统与经典的路易斯酸区分开来。
• Recognition and Site-Selective Transformation of Monosaccharides by Using Copper(II) Catalysis
  作者：I-Hon Chen、Kevin G. M. Kou、Diane N. Le、Colin M. Rathbun、Vy M. Dong

  DOI：10.1002/chem.201400133

  日期：2014.4.22

  We demonstrate copper(II)‐catalyzed acylation and tosylation of monosaccharides. Various carbohydrate derivatives, including glucopyranosides and ribofuranosides, are obtained in high yields and regioselectivities. Using this versatile strategy, the site of acylation can be switched by choice of ligand. Preliminary mechanistic studies support nucleophilic addition of a copper–sugar complex to the acyl

  我们证明了铜（II）催化的单糖酰化和甲苯磺酸化。以高收率和区域选择性获得了各种碳水化合物衍生物，包括吡喃葡萄糖苷和核呋喃糖苷。使用这种通用策略，可以通过选择配体来切换酰化位点。初步的机理研究支持将铜糖复合物亲核加到酰氯中是限制营业额的。
• Synthesis of Defined and Functionalized Glycans of Lipoteichoic Acid: A Cell Surface Polysaccharide from <i>Clostridium difficile</i>
  作者：Kang Yu、Ningning Bi、Chenghe Xiong、Shuihong Cai、Zhongzhu Long、Zhongwu Guo、Guofeng Gu

  DOI：10.1021/acs.orglett.7b01242

  日期：2017.6.16

  Two structurally defined, functionalized glycans of lipoteichoic acid (LTA, also known as PS-III) from C. difficile, which have one or two repeating units of LTA linked to the core trisaccharide, were efficiently synthesized via a convergent [2 + 3] or [2 + 2 + 3] strategy. The α-linkage of both N-acetylglucosamine residues in the repeating unit were constructed with glycosyl imidates of azidosugars

  通过收敛[2 + 3]有效地合成了两个来自艰难梭菌的结构定义，功能化的脂蛋白酸（LTA，也称为PS-III）聚糖，它们具有一个或两个LTA重复单元与核心三糖相连。或[2 + 2 + 3]策略。重复单元中的两个N-乙酰氨基葡糖残基的α-键均以叠氮糖的糖基酰亚胺为供体而构建，而寡糖之间的磷酸二酯桥是通过H-膦酸酯化学法形成的。两种合成靶标均在核心三糖还原端含有一个3-氨丙基，这有助于它们与其他生物分子结合，从而提供可用于各种生物学研究和应用的结合物。
• Efficient Preparation of 2‐SAc‐Glycosyl Donors and Investigation of Their Application in the Synthesis of 2‐Deoxyglycosides
  作者：Tao Luo、Qiang Zhang、Yang‐Fan Guo、Zhi‐Chao Pei、Hai Dong

  DOI：10.1002/ejoc.202200533

  日期：2022.7.14

  We have developed efficient strategies for the synthesis of glycosyl donors with 2-thioacetyl (SAc) groups in order to synthesize 2-deoxysugars with absolute α/β configuration.

  我们开发了合成具有 2-硫乙酰 (SAc) 基团的糖基供体的有效策略，以合成具有绝对 α/β 构型的 2-脱氧糖。
• Simple and efficient per-O-acetylation of carbohydrates by lithium perchlorate catalyst
  作者：Kuo-Cheng Lu、Shu-Yi Hsieh、Laxmikant N. Patkar、Chien-Tien Chen、Chun-Cheng Lin

  DOI：10.1016/j.tet.2004.06.138

  日期：2004.9

  Lithium perchlorate is demonstrated to be a highly efficient and convenient catalyst for the per-O-acetylation of various saccharides with excellent yields. (C) 2004 Elsevier Ltd. All rights reserved.