methyl (2S,3R,4S,5S)-8-[bis(2,2,2-trifluoroethoxy)-phosphoryl]-3,5-bis-(t-butyldimethylsilyloxy)-2,4-dimethyl-7-oxo-octanoate | 858948-08-0

• 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 (2S,3R,4S,5S)-8-[bis(2,2,2-trifluoroethoxy)-phosphoryl]-3,5-bis-(t-butyldimethylsilyloxy)-2,4-dimethyl-7-oxo-octanoate
• 英文别名: methyl (2R,3S,4S,5S)-8-[bis(2,2,2-trifluoroethoxy)phosphoryl]-3,5-bis[[tert-butyl(dimethyl)silyl]oxy]-2,4-dimethyl-7-oxooctanoate
• CAS: 858948-08-0
• 化学式: C₂₇H₅₁F₆O₈PSi₂
• 分子量: 704.832
• InChiKey: BXHDJPOCIYOIME-MXNKGDRCSA-N

物化性质

• 沸点：
  574.5±50.0 °C(predicted)
• 密度：
  1.118±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  8.52
• 重原子数：
  44
• 可旋转键数：
  19
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  97.4
• 氢给体数：
  0
• 氢受体数：
  14

反应信息

• 作为反应物：
  描述：

  (2R,3R,4S,5Z,8S,9R,10R,11S,12S,13Z)-3,9-bis[[tert-butyl(dimethyl)silyl]oxy]-11-[(4-methoxyphenyl)methoxy]-2,4,6,8,10,12-hexamethylhexadeca-5,13,15-trienal 、 methyl (2S,3R,4S,5S)-8-[bis(2,2,2-trifluoroethoxy)-phosphoryl]-3,5-bis-(t-butyldimethylsilyloxy)-2,4-dimethyl-7-oxo-octanoate 在 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 反应 0.5h， 以73%的产率得到methyl (2R,3S,4S,5S,8Z,10S,12S,13Z,16S,17R,18S,19S,20S,21Z)-3,5,11,17-tetrakis(t-butyldimethylsilyloxy)-19-(4-methoxybenzyloxy)-2,4,10,12,14,16,18,20-octamethyl-7-oxo-tetracosa-8,13,21,23-tetraenoate
  参考文献：
  名称：

  Development of a Third-Generation Total Synthesis of (+)-Discodermolide:  An Expedient Still−Gennari-Type Fragment Coupling Utilizing an Advanced β-Ketophosphonate

  摘要：

  A novel total synthesis of the complex polyketide discodermolide, a promising anticancer agent of marine sponge origin, has been completed in 11.1% overall yield over 21 linear steps. This third-generation approach features an unprecedented Still-Gennari-type HWE olefination reaction between advanced C1-C8 beta-ketophosphonate 61 and C9-C24 aldehyde 7, introducing the (8z)alkene with 10:1 selectivity. The stereotetrad found in the C1-C8 subunit 61 was established via a highly diastereoselective boron-mediated aldol reaction/in situ reduction between ketone (S)-8 and 3-benzyloxypropanal. The (7S)-configuration was installed by the reduction of enone 73 with K-Selectride.

  DOI：

  10.1021/jo050481a
• 作为产物：
  描述：

  methyl (2R,3S,4S,5S)-3,5-bis[[tert-butyl(dimethyl)silyl]oxy]-7-chloro-2,4-dimethyl-7-oxoheptanoate 、 双(2,2,2-三氟乙基)甲基磷酸酯 在 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 为溶剂， 反应 1.0h， 以260 mg的产率得到methyl (2S,3R,4S,5S)-8-[bis(2,2,2-trifluoroethoxy)-phosphoryl]-3,5-bis-(t-butyldimethylsilyloxy)-2,4-dimethyl-7-oxo-octanoate
  参考文献：
  名称：

  Development of a Third-Generation Total Synthesis of (+)-Discodermolide:  An Expedient Still−Gennari-Type Fragment Coupling Utilizing an Advanced β-Ketophosphonate

  摘要：

  A novel total synthesis of the complex polyketide discodermolide, a promising anticancer agent of marine sponge origin, has been completed in 11.1% overall yield over 21 linear steps. This third-generation approach features an unprecedented Still-Gennari-type HWE olefination reaction between advanced C1-C8 beta-ketophosphonate 61 and C9-C24 aldehyde 7, introducing the (8z)alkene with 10:1 selectivity. The stereotetrad found in the C1-C8 subunit 61 was established via a highly diastereoselective boron-mediated aldol reaction/in situ reduction between ketone (S)-8 and 3-benzyloxypropanal. The (7S)-configuration was installed by the reduction of enone 73 with K-Selectride.

  DOI：

  10.1021/jo050481a