methyl 6'-deoxy-6'-fluoro-2,2',3,3',4',6-hexa-O-mesitoyl-β-lactoside | 141485-06-5

• 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-2,2',3,3',4',6-hexa-O-mesitoyl-β-lactoside
• CAS: 141485-06-5
• 化学式: C₇₃H₈₃FO₁₆
• 分子量: 1235.45
• InChiKey: XHHDRXUTYBBTMK-BRLWDBMGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  12.97
• 重原子数：
  90.0
• 可旋转键数：
  17.0
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  194.72
• 氢给体数：
  0.0
• 氢受体数：
  16.0

反应信息

• 作为反应物：
  描述：

  methyl 6'-deoxy-6'-fluoro-2,2',3,3',4',6-hexa-O-mesitoyl-β-lactoside 在 lithium aluminium tetrahydride 作用下， 以 1,4-二氧六环 为溶剂， 反应 2.0h， 以70%的产率得到methyl 6'-deoxy-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'-O-butyryl-2,2',3,3',4',6-hexa-O-mesitoyl-β-lactoside 在 sodium hydroxide 、 4,4'-二氨基二苯乙烯-2,2'-二磺酸 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 1.5h， 生成 methyl 6'-deoxy-6'-fluoro-2,2',3,3',4',6-hexa-O-mesitoyl-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