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.
• Nucleosides. 116. 1-(.beta.-D-Xylofuranosyl)-5-fluorocytosines with a leaving group on the 3' position. Potential double-barreled masked precursors of anticancer nucleosides
  作者：K. A. Watanabe、U. Reichman、C. K. Chu、D. H. Hollenberg、J. J. Fox

  DOI：10.1021/jm00184a006

  日期：1980.10

  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.
• Influence of the stereochemistry of sugars on the selectivity of formation of carbohydrate-derived cyclopentadienyl and indenyl ligands
  作者：Richard La?、Sandrine Martin、Renaud Touret

  DOI：10.1039/b517146f

  日期：——

  Interaction of lithium cyclopentadienide with a suitable partially protected α-D-allofuranose triflate, 4, epimer at C3 of glucose, gives as a major product, besides the expected glucose-cyclopentadiene, 5, a glucose-disubstituted cyclopentadiene, 6. This unprecedented behaviour, which does not occur with α-D-glucofuranose and other sugars, is tentatively explained by a complexation of LiCp and the oxygen atoms of the isopropylidene function of one molecule of 4 and one of 5, giving a termolecular structure as the result of a template effect. The results of other experiments, such as the use of MgCp2 in place of LiCp or the complexation of oxygen atoms by lithium triflate, which changed the selectivity of the reaction largely in favour of the monosubstitution product 5, support this hypothesis. When lithium indenide is reacted with 4, glucose-monosubstituted and glucose-disubstituted indenes, 8 and 9, respectively, are formed, and 9 is obtained with almost total diastereoselectivity. This result can also be rationalised by a stereoselective complexation of lithium, as shown by separate experiments and by molecular mechanics calculations. Methyltricarbonyl molybdenum(II) complexes have been synthesised and characterised from glucose-monosubstituted 5 and glucose-disubstituted 6 cyclopentadienes.

  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。