methyl (2S,3S,5S,6S)-6-(3-bromo-2,5-diisopropoxy-6-methoxyphenyl)-3-hydroxy-5-methyltetrahydro-2H-pyran-2-carboxylate | 1033591-54-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl (2S,3S,5S,6S)-6-(3-bromo-2,5-diisopropoxy-6-methoxyphenyl)-3-hydroxy-5-methyltetrahydro-2H-pyran-2-carboxylate
• 英文别名: methyl (2S,3S,5S,6S)-6-[5-bromo-2-methoxy-3,6-di(propan-2-yloxy)phenyl]-3-hydroxy-5-methyloxane-2-carboxylate
• CAS: 1033591-54-6
• 化学式: C₂₁H₃₁BrO₇
• 分子量: 475.377
• InChiKey: RIFDGYMUXAIQDB-YWKPPDPDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.6
• 重原子数：
  29
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  83.4
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  methyl (2S,3S,5S,6S)-6-(3-bromo-2,5-diisopropoxy-6-methoxyphenyl)-3-hydroxy-5-methyltetrahydro-2H-pyran-2-carboxylate 、 trimethoxonium tetrafluoroborate 在 1,8-双二甲氨基萘 作用下， 以 二氯甲烷 为溶剂， 反应 5.0h， 以95%的产率得到methyl (2S,3S,5S,6S)-6-(3-bromo-2,5-diisopropoxy-6-methoxyphenyl)-3-methoxy-5-methyltetrahydro-2H-pyran-2-carboxylate
  参考文献：
  名称：

  Total Synthesis of the Hsp90 Inhibitor Geldanamycin

  摘要：

  An enantioselective synthesis of the Hsp90 inhibitor geldanamycin was achieved in 20 linear steps and 2.0% overall yield from 2-methoxyhydroquinone. The synthesis is highlighted by a regio- and stereoselective hydroboration reaction; a Sc(OTf)(3)/Et(3)SiH-mediated pyran ring-opening reaction; an enantioselective crotylation to simultaneously install the C8-C9 (E)-trisubstituted olefin, the C10 and C11 stereocenters; a chelation-controlled asymmetric metallated acetylide addition; and an intramolecular copper(I)-mediated aryl amidation reaction to close the 19-membered macrolactam.

  DOI：

  10.1021/ol800749w
• 作为产物：
  描述：

  methyl (2S,5S)-6-(3-bromo-2,5-diisopropoxy-6-methoxyphenyl)-5-methyl-5,6-dihydro-2H-pyran-2-carboxylate 在 dimethyl sulfide borane 、 sodium hydroxide 、 水 、 双氧水 作用下， 以 四氢呋喃 为溶剂， 反应 1.5h， 以75%的产率得到methyl (2S,3S,5S,6S)-6-(3-bromo-2,5-diisopropoxy-6-methoxyphenyl)-3-hydroxy-5-methyltetrahydro-2H-pyran-2-carboxylate
  参考文献：
  名称：

  Total Synthesis of the Hsp90 Inhibitor Geldanamycin

  摘要：

  An enantioselective synthesis of the Hsp90 inhibitor geldanamycin was achieved in 20 linear steps and 2.0% overall yield from 2-methoxyhydroquinone. The synthesis is highlighted by a regio- and stereoselective hydroboration reaction; a Sc(OTf)(3)/Et(3)SiH-mediated pyran ring-opening reaction; an enantioselective crotylation to simultaneously install the C8-C9 (E)-trisubstituted olefin, the C10 and C11 stereocenters; a chelation-controlled asymmetric metallated acetylide addition; and an intramolecular copper(I)-mediated aryl amidation reaction to close the 19-membered macrolactam.

  DOI：

  10.1021/ol800749w

文献信息

• Total Synthesis of the Hsp90 Inhibitor Geldanamycin
  作者：Hua-Li Qin、James S. Panek

  DOI：10.1021/ol800749w

  日期：2008.6.1

  An enantioselective synthesis of the Hsp90 inhibitor geldanamycin was achieved in 20 linear steps and 2.0% overall yield from 2-methoxyhydroquinone. The synthesis is highlighted by a regio- and stereoselective hydroboration reaction; a Sc(OTf)(3)/Et(3)SiH-mediated pyran ring-opening reaction; an enantioselective crotylation to simultaneously install the C8-C9 (E)-trisubstituted olefin, the C10 and C11 stereocenters; a chelation-controlled asymmetric metallated acetylide addition; and an intramolecular copper(I)-mediated aryl amidation reaction to close the 19-membered macrolactam.