3-Brom-3-desoxy-1,2;5,6,-di-O-isopropyliden-α-D-glucofuranose | 14260-29-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3-Brom-3-desoxy-1,2;5,6,-di-O-isopropyliden-α-D-glucofuranose
• 英文别名: 3-bromo-3-deoxy-1,2:5,6-di-O-isopropylidene-α-D-glucofuranose；3-Brom-3-deoxy-1,2:5,6-di-O-isopropyliden-α-D-glucofuranose；(3aR,5R,6S,6aS)-6-bromo-5-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-2,2-dimethyl-3a,5,6,6a-tetrahydrofuro[2,3-d][1,3]dioxole
• CAS: 14260-29-8
• 化学式: C₁₂H₁₉BrO₅
• 分子量: 323.184
• InChiKey: OPASGEPQUZKAFV-JDDHQFAOSA-N

物化性质

• 沸点：
  341.7±42.0 °C(Predicted)
• 密度：
  1.394±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  18
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  46.2
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  3-Brom-3-desoxy-1,2;5,6,-di-O-isopropyliden-α-D-glucofuranose 在 sodium tetrahydroborate 、 sodium periodate 、 硫酸 作用下， 以 甲醇 、 乙醇 为溶剂， 反应 54.0h， 生成 ((3aR,5R,6S,6aS)-6-Bromo-2,2-dimethyl-tetrahydro-furo[2,3-d][1,3]dioxol-5-yl)-methanol
  参考文献：
  名称：

  Nucleosides. 116. 1-(.beta.-D-Xylofuranosyl)-5-fluorocytosines with a leaving group on the 3' position. Potential double-barreled masked precursors of anticancer nucleosides

  摘要：

  Syntheses of five pairs of cytosine and 5-fluorocytosinexylofuranosyl nucleosides in which the 3'-hydroxyl group is replaced by Cl, Br, OMs, or OTs are described. Those xylosyl nucleosides with a good leaving group at the 3' position exhibit good inhibitory activity against L5178Y and P815 mouse leukemic cells in vitro at rather low concentrations, and like that of ara-C this cytotoxicity is reversed by 2'-deoxycytidine but not by thymidine. Xylosylcytosines are not active against ara-C resistant lines of L5178Y and P815 cells; however, the corresponding 5-fluorocytosine analogues exhibit significant cytotoxicity against these ara-C resistant leukemic cell lines, and this activity is reversed by thmidine but not by deoxycytidine. These data support the "double-barreled" masked precursor hypothesis in that xylosyl-5-fluorocytosines substituted at the 3' position by a good leaving group exhibit activity akin to that of ara-C in the ara-C sensitive lines, while these nucleosides act as 5-fluoropyrimidines in the ara-C resistant lines.

  DOI：

  10.1021/jm00184a006
• 作为产物：
  描述：

  1,2:5,6-di-O-isopropylidene-3-O-trifluoromethanesulfonyl-α-D-allofuranose 在 lithium cyclopentadienide 、 lithium bromide 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 为溶剂， 以100%的产率得到3-Brom-3-desoxy-1,2;5,6,-di-O-isopropyliden-α-D-glucofuranose
  参考文献：
  名称：

  Influence of the stereochemistry of sugars on the selectivity of formation of carbohydrate-derived cyclopentadienyl and indenyl ligands

  摘要：

  环戊二烯锂与适当的部分受保护的 α-D-allofuranose triflate（4，葡萄糖 C3 的缩合物）相互作用，除了得到预期的葡萄糖-环戊二烯（5）外，还得到葡萄糖-二取代环戊二烯（6）作为主要产物。α-D-呋喃葡萄糖和其他糖类不会出现这种前所未有的现象，初步解释是 LiCp 与 4 和 5 分子中一个分子的异亚丙基官能团的氧原子发生了络合反应，从而产生了作为模板效应结果的三分子结构。其他实验的结果，如使用 MgCp2 代替 LiCp 或用三酸锂络合氧原子，在很大程度上改变了反应的选择性，有利于单取代产物 5，也支持了这一假设。当茚化锂与 4 反应时，分别生成葡萄糖一取代茚和葡萄糖二取代茚，即 8 和 9，并以几乎完全的非对映选择性得到 9。这一结果也可以通过锂的立体选择性络合得到合理解释，正如单独的实验和分子力学计算所显示的那样。以葡萄糖一取代的 5 环戊二烯和葡萄糖二取代的 6 环戊二烯为原料，合成了甲基三羰基钼（II）配合物，并对其进行了表征。

  DOI：

  10.1039/b517146f

文献信息

• Kunz, Horst; Schmidt, Peter, Liebigs Annalen der Chemie, 1982, # 7, p. 1245 - 1260
  作者：Kunz, Horst、Schmidt, Peter

  DOI：——

  日期：——
• Aldotetroses and C(3)-Modified Aldohexoses as Substrates for N-Acetylneuraminic Acid Aldolase: A Model for the Explanation of the Normal and the Inversed Stereoselectivity
  作者：Wolfgang Fitz、Jan-Robert Schwark、Chi-Huey Wong

  DOI：10.1021/jo00117a016

  日期：1995.6

  The four stereoisomeric aldotetroses were accepted with different reactivities by N-acetylneuraminic acid aldolase. C(3)-modified D-mannose and D-glucose derivatives, respectively, failed to undergo enzymatic aldol addition. Based on the observed reactivities of the tested compounds (about 58), a mechanistic scheme is proposed which relates substrate structure, reactivity and stereochemical outcome observed in Neu5Ac aldolase-catalyzed reactions. The condensation products obtained in the L-erythrose and D-threose reactions are side-chain modified sialic acid and D-KDO derivatives, respectively, of biological interest.