benzyl [fluoro 3-deoxy-4,5-7,8-di-O-isopropylidene-α-D-manno-octulopyranosid]onate | 114827-01-9

• 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: benzyl [fluoro 3-deoxy-4,5-7,8-di-O-isopropylidene-α-D-manno-octulopyranosid]onate
• 英文别名: benzyl (3-deoxy-4,5:7,8-di-O-isopropylidene-α-D-manno-oct-2-ulopyranosyl)onate fluoride；benzyl (3aR,4R,6S,7aR)-4-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-6-fluoro-2,2-dimethyl-3a,4,7,7a-tetrahydro-[1,3]dioxolo[4,5-c]pyran-6-carboxylate
• CAS: 114827-01-9
• 化学式: C₂₁H₂₇FO₇
• 分子量: 410.44
• InChiKey: YLBDDVZBBNCLLJ-WUKWMOGPSA-N

物化性质

• 沸点：
  460.4±45.0 °C(predicted)
• 密度：
  1.27±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.86
• 重原子数：
  29.0
• 可旋转键数：
  4.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  72.45
• 氢给体数：
  0.0
• 氢受体数：
  7.0

反应信息

• 作为反应物：
  描述：

  benzyl [fluoro 3-deoxy-4,5-7,8-di-O-isopropylidene-α-D-manno-octulopyranosid]onate 在 三氟化硼乙醚 、 水 、 溶剂黄146 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 生成 benzyl [N-benzyloxycarbonyl-3-aminopropyl-3-deoxy-α-D-manno-octulopyranosid]onate
  参考文献：
  名称：

  Chemical Synthesis and Immunological Evaluation of the Inner Core Oligosaccharide of Francisella tularensis

  摘要：

  Francisella tularensis, which is a Gram negative bacterium that causes tularemia, has been classified by the Center for Disease Control and Prevention (CDC) as a category A bioweapon. The development of vaccines, immunotherapeutics, and diagnostics for F. tularensis requires a detailed knowledge of the saccharide structures that can be recognized by protective antibodies. We have synthesized the inner core region of the lipopolysaccharide (LPS) of F. tularensis to probe antigenic responses elicited by a live and subunit vaccine. The successful preparation of the target compound relied on the use of a disaccharide which was modified by the orthogonal protecting groups diethylisopropylsilyl (DEIPS), 2-naphthylmethyl (Nap), allyl ether (All), and levulinoyl (Lev) ester. The ability to remove the protecting groups in different orders made it possible to establish the optimal glycosylations sequence to prepare a highly crowded 1,2,3-cis configured branching point. A variety of different methods were exploited to control anomeric selectivities of the glycosylations. A comparison of the H-1 NMR spectra of isolated material and the synthetic derivative confirmed the reported structural assignment of the inner core oligosaccharide of F. tularensis. The observation that immunizations with LPS lead to antibody responses to the inner core saccharides provides an impetus to further explore this compound as a vaccine candidate.

  DOI：

  10.1021/ja306274v
• 作为产物：
  描述：

  2,3,5,6-di-isopropyIidene-1,4-dihydroxy-D-mannitol 在 六甲基磷酰三胺 、 ruthenium trichloride 、 sodium periodate 、 N-溴代丁二酰亚胺(NBS) 、 氯化亚砜 、 二乙胺基三氟化硫 、 水 、 三乙胺 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 二氯甲烷 、 丙酮 、 乙腈 为溶剂， 反应 1.92h， 生成 benzyl [fluoro 3-deoxy-4,5-7,8-di-O-isopropylidene-α-D-manno-octulopyranosid]onate
  参考文献：
  名称：

  Chemical Synthesis and Immunological Evaluation of the Inner Core Oligosaccharide of Francisella tularensis

  摘要：

  Francisella tularensis, which is a Gram negative bacterium that causes tularemia, has been classified by the Center for Disease Control and Prevention (CDC) as a category A bioweapon. The development of vaccines, immunotherapeutics, and diagnostics for F. tularensis requires a detailed knowledge of the saccharide structures that can be recognized by protective antibodies. We have synthesized the inner core region of the lipopolysaccharide (LPS) of F. tularensis to probe antigenic responses elicited by a live and subunit vaccine. The successful preparation of the target compound relied on the use of a disaccharide which was modified by the orthogonal protecting groups diethylisopropylsilyl (DEIPS), 2-naphthylmethyl (Nap), allyl ether (All), and levulinoyl (Lev) ester. The ability to remove the protecting groups in different orders made it possible to establish the optimal glycosylations sequence to prepare a highly crowded 1,2,3-cis configured branching point. A variety of different methods were exploited to control anomeric selectivities of the glycosylations. A comparison of the H-1 NMR spectra of isolated material and the synthetic derivative confirmed the reported structural assignment of the inner core oligosaccharide of F. tularensis. The observation that immunizations with LPS lead to antibody responses to the inner core saccharides provides an impetus to further explore this compound as a vaccine candidate.

  DOI：

  10.1021/ja306274v

文献信息

• Rhamnogalacturonan II: Chemical Synthesis of a Substructure Including α‐2,3‐Linked Kdo**
  作者：Enzo Mancuso、Cecilia Romanò、Nino Trattnig、Philipp Gritsch、Paul Kosma、Mads H. Clausen

  DOI：10.1002/chem.202100837

  日期：2021.4.26

  The synthesis of a fully deprotected Kdo‐containing rhamnogalacturonan II pentasaccharide is described. The strategy relies on the preparation of a suitably protected homogalacturonan tetrasaccharide backbone, through a post‐glycosylation oxidation approach, and its stereoselective glycosylation with a Kdo fluoride donor.

  描述了完全脱保护的含Kdo的鼠李半乳糖醛酸聚糖II五糖的合成。该策略依赖于通过糖基化后氧化方法制备适当保护的高半乳糖醛酸四糖骨架，以及其与Kdo氟化物供体的立体选择性糖基化。
• Synthetic approach to bacterial lipopolysaccharide, preparation of trisaccharide part structures containing KDO and 1-dephospho lipid A
  作者：Masahiro Imoto、Naoto Kusunose、Shoichi Kusumoto、Tetsuo Shiba

  DOI：10.1016/s0040-4039(00)86718-0

  日期：——
• IMOTO, MASAHIRO;KUSUNOSE, NAOTO;MATSUURA, YOSHIKI;KUSUMOTO, SHOICHI;SHIBA+, TETRAHEDRON LETT., 28,(1987) N 50, 6277-6280
  作者：IMOTO, MASAHIRO、KUSUNOSE, NAOTO、MATSUURA, YOSHIKI、KUSUMOTO, SHOICHI、SHIBA+

  DOI：——

  日期：——
• Chemical synthesis of 1-dephospho derivative of escherichia coli re lipopolysaccharide
  作者：Shoichi Kusumoto、Naoto Kusunose、Takashi Kamikawa、Tetsuo Shiba

  DOI：10.1016/s0040-4039(00)82337-0

  日期：1988.1