Methyl 6'-deoxy-6'-fluoro β-lactoside | 141485-07-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: Methyl 6'-deoxy-6'-fluoro β-lactoside
• 英文别名: methyl 6'-deoxy-6'-fluoro-β-lactaside；methyl 6'-deoxy-6'-fluoro-β-lactoside；Gal6F(b1-4)b-Glc1Me；(2R,3R,4S,5R,6S)-2-[(2R,3S,4R,5R,6R)-4,5-dihydroxy-2-(hydroxymethyl)-6-methoxyoxan-3-yl]oxy-6-(fluoromethyl)oxane-3,4,5-triol
• CAS: 141485-07-6
• 化学式: C₁₃H₂₃FO₁₀
• 分子量: 358.318
• InChiKey: CDTYFCZMYMYSSA-ABBMIVAOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -3.7
• 重原子数：
  24
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  158
• 氢给体数：
  6
• 氢受体数：
  11

反应信息

• 作为反应物：
  描述：

  乙酸酐 、 Methyl 6'-deoxy-6'-fluoro β-lactoside 在 吡啶 作用下， 以94%的产率得到methyl 2,2',3,3,4',6-hexa-O-acetyl-6'-deoxy-6'-fluoro-β-lactoside
  参考文献：
  名称：

  Application of protease-catalyzed regioselective esterification in synthesis of 6'-deoxy-6'-fluoro- and 6-deoxy-6-fluorolactosides

  摘要：

  Subtilisin-catalyzed esterification of methyl 4-O-beta-D-galactopyranosyl-beta-D-glucopyranoside (methyl beta-lactoside) (1) with 2,2,2-trichloroethyl butyrate (3) distinguished between the two primary hydroxyl groups of 1, yielding exclusively the 6'-O-monobutyryl derivative 6 from which 6'-deoxy-6'-fluoro- and 6-deoxy-6-fluorolactosides (22 and 29, respectively) were efficiently synthesized. A key feature in the synthesis of 22 was the use of the 2,4,6-trimethylbenzoyl (mesitoyl) group to protect the remaining free hydroxyl groups. A mesitoate ester, in addition to being inert to the condition that hydrolyzed a butyrate ester, could be easily cleaved by reduction with AlH3 without hydrogenolysis of a C-F bond. The steric bulk of a mesitoyl group suppressed the C-4' --> C-6' acyl migration during the fluorination with (diethylamino)sulfur trifluoride (DAST). The success in the synthesis of 29 depended on the choice of solvent employed for the DAST fluorination. With diglyme the desired 6-fluoro derivative 28 was the only product, whereas the use of CH2Cl2 yielded 6-O-methyl-beta-lactosyl fluoride 30 concomitantly through a C-1 --> C-6 migration of the methoxyl group.

  DOI：

  10.1021/jo00038a036
• 作为产物：
  描述：

  methyl 6'-deoxy-6'-fluoro-2,2',3,3',4',6-hexa-O-mesitoyl-β-lactoside 在 aluminium hydride 作用下， 以 乙醚 为溶剂， 反应 0.25h， 以72%的产率得到Methyl 6'-deoxy-6'-fluoro β-lactoside
  参考文献：
  名称：

  Application of protease-catalyzed regioselective esterification in synthesis of 6'-deoxy-6'-fluoro- and 6-deoxy-6-fluorolactosides

  摘要：

  Subtilisin-catalyzed esterification of methyl 4-O-beta-D-galactopyranosyl-beta-D-glucopyranoside (methyl beta-lactoside) (1) with 2,2,2-trichloroethyl butyrate (3) distinguished between the two primary hydroxyl groups of 1, yielding exclusively the 6'-O-monobutyryl derivative 6 from which 6'-deoxy-6'-fluoro- and 6-deoxy-6-fluorolactosides (22 and 29, respectively) were efficiently synthesized. A key feature in the synthesis of 22 was the use of the 2,4,6-trimethylbenzoyl (mesitoyl) group to protect the remaining free hydroxyl groups. A mesitoate ester, in addition to being inert to the condition that hydrolyzed a butyrate ester, could be easily cleaved by reduction with AlH3 without hydrogenolysis of a C-F bond. The steric bulk of a mesitoyl group suppressed the C-4' --> C-6' acyl migration during the fluorination with (diethylamino)sulfur trifluoride (DAST). The success in the synthesis of 29 depended on the choice of solvent employed for the DAST fluorination. With diglyme the desired 6-fluoro derivative 28 was the only product, whereas the use of CH2Cl2 yielded 6-O-methyl-beta-lactosyl fluoride 30 concomitantly through a C-1 --> C-6 migration of the methoxyl group.

  DOI：

  10.1021/jo00038a036

文献信息

• Syntheses of all the possible monomethyl ethers and several deoxyhalo analogues of methyl β-lactoside as ligands for the Ricinus communis lectins
  作者：Paloma Fernández、Jesús Jiménez-Berbero、Manuel Martín-Lomas

  DOI：10.1016/0008-6215(94)84243-4

  日期：1994.2

  The synthesis of all the possible monomethyl ethers of methyl beta-lactoside (1) has been performed from 1 in a straightforward way, making use of the different reactivity of the hydroxyl groups in alkylation and stannylation reactions. In addition, the deoxyfluoro derivatives of 1 at positions, 6,3',4',epi-4', and 6' have been prepared by reaction of the appropriate substrates with diethylaminosulfur

  甲基β-内酯（1）的所有可能的单甲基醚的合成已从1直接进行，利用了烷基化和甲锡烷基化反应中羟基的不同反应性。另外，通过适当的底物与二乙基氨基三氟化硫或氟化四丁基铵的反应制备了在6,3'，4'，epi-4'和6'位置的1的脱氧氟衍生物。最后，还制备了1的6-脱氧碘和6'-溴脱氧氧基类似物。