methyl (2R,3R,E)-3-(dimethyl(phenyl)silyl)-2-(methoxymethoxy)-3-methylhex-4-enoate | 1033591-44-4

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: methyl (2R,3R,E)-3-(dimethyl(phenyl)silyl)-2-(methoxymethoxy)-3-methylhex-4-enoate
• 英文别名: methyl (E,2R,3R)-3-[dimethyl(phenyl)silyl]-2-(methoxymethoxy)-3-methylhex-4-enoate
• CAS: 1033591-44-4
• 化学式: C₁₈H₂₈O₄Si
• 分子量: 336.503
• InChiKey: COGOJPRFFBHGSI-RZJCNXBPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  23
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  methyl (2R,3R,E)-3-(dimethyl(phenyl)silyl)-2-(methoxymethoxy)-3-methylhex-4-enoate 、 (2S,4R)-5-(3-bromo-2,5-diisopropoxy-6-methoxyphenyl)-2-methoxy-4-methylpentanal 、 苄氧基三甲基硅烷 在 三氟化硼乙醚 作用下， 以 二氯甲烷 为溶剂， 反应 73.0h， 以70%的产率得到methyl (2S,5S,6R,7S,9R,E)-6-(benzyloxy)-10-(3-bromo-2,5-diisopropoxy-6-methoxyphenyl)-7-methoxy-2-(methoxymethoxy)-3,5,9-trimethyldec-3-enoate
  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：

  (E)-(2R,3R)-3-(dimethyl-phenyl-silanyl)-2-hydroxy-3-methyl-hex-4-enoic acid methyl ester 、 氯甲基甲基醚 在 N,N-二异丙基乙胺 作用下， 以 二氯甲烷 为溶剂， 以86%的产率得到methyl (2R,3R,E)-3-(dimethyl(phenyl)silyl)-2-(methoxymethoxy)-3-methylhex-4-enoate
  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.