methyl 6-O-(tert-butyldiphenylsilyl)-3,4-O-isopropylidene-β-D-galactopyranoside | 114244-04-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氧吡喃
• 英文名称: methyl 6-O-(tert-butyldiphenylsilyl)-3,4-O-isopropylidene-β-D-galactopyranoside
• 英文别名: methyl 6-O-(tert-butyldiphenylsilyl)-2-hydroxyl-3,4-O-isopropylidene-β-D-galactopyranoside；(3aS,4R,6R,7R,7aR)-4-[[tert-butyl(diphenyl)silyl]oxymethyl]-6-methoxy-2,2-dimethyl-4,6,7,7a-tetrahydro-3aH-[1,3]dioxolo[4,5-c]pyran-7-ol
• CAS: 114244-04-1
• 化学式: C₂₆H₃₆O₆Si
• 分子量: 472.654
• InChiKey: HNLVRGKVSUNDEF-GNADVCDUSA-N

物化性质

• 沸点：
  536.6±50.0 °C(predicted)
• 密度：
  1.15±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.82
• 重原子数：
  33
• 可旋转键数：
  7
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  66.4
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  methyl 6-O-(tert-butyldiphenylsilyl)-3,4-O-isopropylidene-β-D-galactopyranoside 在 吡啶 、 盐酸 、 四丁基氟化铵 、 sodium hydride 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 水 、 mineral oil 为溶剂， 反应 79.5h， 生成
  参考文献：
  名称：

  Copper‐Catalyzed Stereoselective Borylation and Palladium‐Catalyzed Stereospecific Cross‐Coupling to Give Aryl C ‐Glycosides

  摘要：

  AbstractMetabolically stable C‐glycosides are an essential family of compounds in bioactive natural products, therapeutic agents, and biological probes. For their application, development of synthetic methods by connecting glycosides and aglycons with strict stereocontrol at the anomeric carbon, as well as with high functional‐group compatibility and environmental compatibility is a pivotal issue. Although Suzuki–Miyaura‐type C(sp3)−C(sp2) cross‐coupling using glycosyl boronates is a potential candidate for the construction of C‐glycosides, neither the cross‐coupling itself nor the facile synthesis of the coupling precursor, glycosyl boronates, have been achieved to date. Herein, it was succeeded to develop a copper‐catalyzed stereoselective one‐step borylation of glycosyl bromides to glycosyl boronates and palladium‐catalyzed stereospecific cross‐coupling of β‐glycosyl borates with aryl bromides to give aryl β‐C‐glycosides, in which the β‐configuration of the anomeric carbon of the glycosyl trifluoroborates is stereoretentively transferred to that of the resulting aryl C‐glycosides.

  DOI：

  10.1002/chem.202203376
• 作为产物：
  描述：

  甲基-Β-D-吡喃半乳糖苷 在 吡啶 、 4-二甲氨基吡啶 、 混旋樟脑磺酸 作用下， 以 丙酮 为溶剂， 生成 methyl 6-O-(tert-butyldiphenylsilyl)-3,4-O-isopropylidene-β-D-galactopyranoside
  参考文献：
  名称：

  D-半乳糖基溶血磷脂作为磷脂酰肌醇磷酸激酶的选择性底物和非 ATP 竞争性抑制剂的合理设计和合成

  摘要：

  New-to-Nature D-半乳糖基溶血磷脂经过合理设计和合成，可作为磷脂酰肌醇磷酸激酶的人工底物和非 ATP 竞争性抑制剂，磷脂酰肌醇磷酸激酶是经过验证的致命人类疾病（包括癌症、肌萎缩侧索硬化和 SARS- COVID-2 感染。D-半乳糖基溶血磷脂作为磷脂酰肌醇磷酸激酶的选择性底物和非 ATP 竞争性抑制剂的合理设计和合成（X. Huang、J. Hu 等人）

  DOI：

  10.1002/chem.202202083

文献信息

• Synthesis of intermediates for stereospecific synthesis of α- and β-C-nucleosides: Ring contraction of protected 2-0-trifluoromethanesulphonates of galacto- and altro-pyranosides
  作者：George W.J Fleet、Liza C Seymour

  DOI：10.1016/s0040-4039(00)96272-5

  日期：——

  4-0-isopropylidene-2-0-trifluoromethanesulphonyl-D-galactopyranosides and with methyl 6-0-(-butyldiphenyl)silyl-3,4-0-isopropylidene-2-0-trifluoromethane-sulphonyl-α-D-altropyranoside give, respectively, intermediates suitable for the stereospecific synthesis of α- and β-C-nucleosides.

  叠氮化钠与甲基6-0-（-丁基二苯基）甲硅烷基-3,4-0-异亚丙基-2-0-三氟甲磺酰基-D-吡喃半乳糖苷与甲基6-0-（-丁基二苯基）甲硅烷基-3,4的反应-0-异亚丙基-2-0-三氟甲烷-磺酰基-α-D-阿托吡喃糖苷分别提供适合于立体定向合成α-和β-C-核苷的中间体。
• Synthesis of O-α-l-fucopyranosyl-(1→3)-O-β-d-galactopyranosyl-(1→4)-2-acetamido-2-deoxy-d-glucopyranose (N-acetyl-3′-O-α-l-fucopyranosyllactosamine)
  作者：Raschmi Dubey、Donna Reynolds、Saeed A. Abbas、Khushi L. Matta

  DOI：10.1016/0008-6215(88)84070-9

  日期：1988.12

  Abstract Methyl 2- O -benzyl-β- d -galactopyranoside ( 6 ) was obtained in five, good yielding steps from methyl β- d -galactopyranoside ( 1 ). Treatment of 1 with tert -butylchlorodiphenylsilane in N,N -dimethylformamide in the presence of imidazole afforded a 6-( tert -butyldiphenylsilyl) ether, which was converted into its 3,4- O -isopropylidene derivative ( 3 ). Benzylation of 3 with benzyl bromide-silver

  摘要从甲基β-d-吡喃半乳糖苷（1）分五个步骤，以良好的收率得到了甲基2-O-苄基-β-d-吡喃半乳糖苷（6）。在咪唑存在下，在N，N-二甲基甲酰胺中用叔丁基氯二苯基硅烷处理1，得到6-（叔丁基二苯基甲硅烷基）醚，将其转化为其3,4-O-异亚丙基衍生物（3）。3用苄基溴化银在N，N-二甲基甲酰胺中进行苯甲酰化，然后将其缩醛和醚基裂解，得到6。在相似的苄基化后，接着相同的脱保护序列，苄基2-乙酰氨基-3,6-二-O-苄基-4-O- [6-O-（叔丁基二苯基甲硅烷基）-3,4-O-异亚丙基- β-d-吡喃半乳糖基] -2-脱氧-α-d-吡喃葡萄糖苷得到2-O-苄基衍生物（10）。将化合物10转化为其4，6-O-亚苄基乙缩醛（11）。用2,3,4-三-O-苄基-α-1-呋喃果糖基溴化物将11的糖基化（通过卤离子催化）提供了完全保护的三糖衍生物（13）。裂解亚苄基，然后裂解13的苄基，得到标题三糖（16）。16的结构由13
• Highly Selective β-Mannosylations and β-Rhamnosylations Catalyzed by Bis-thiourea
  作者：Qiuhan Li、Samuel M. Levi、Eric N. Jacobsen

  DOI：10.1021/jacs.0c04255

  日期：2020.7.8

  We report highly beta-selective bis-thioureas-catalyzed 1,2-cis-O-pyranosylations employing easily accessible acetonide-protected donors. A wide variety of alcohol nucleophiles, including complex natural products, glycosides, and amino acids were beta-mannosylated and beta-rhamnosylated successfully using an operationally simple protocol under mild and neutral conditions. Less nucleophilic acceptors such as phenols were also glycosylated efficiently in excellent yields and with high beta-selectivities.
• Synthesis of a core disaccharide from the Streptococcus pneumoniae type 23F capsular polysaccharide antigen
  作者：Somnath Dasgupta、Mark Nitz

  DOI：10.1016/j.carres.2010.08.002

  日期：2010.10

  The synthesis of methyl alpha-L-rhamnopyranosyl-(1 -> 2)-beta-D-galactopyranoside and methyl alpha-L-rhamnopyranosyl-(1 -> 2)-3-(glycer-2-yl-phosphate)-beta-D-galactopyranoside disaccharides from the Streptococcus pneumoniae type 23F capsular polysaccharide is reported. A simple protecting group strategy was followed using commercially available monosaccharides and phosphorylating reagents. H-Phosphonate and phosphoramidite coupling chemistries were explored for introducing the phosphodiester. Hydrazine hydrate was found to be a mild and efficient deacetylating agent, which was required to avoid phosphate migration during the deprotection of the phosphodiester functionalized disaccharide. (C) 2010 Elsevier Ltd. All rights reserved.
• FLEET, GEORGE W. J.;SEYMOUR, LIZA C., TETRAHEDRON LETT., 28,(1987) N 26, 3015-3018
  作者：FLEET, GEORGE W. J.、SEYMOUR, LIZA C.

  DOI：——

  日期：——