methyl (2Z)-2-[(1R,4S,5R,6R)-5,6-bis[[tert-butyl(diphenyl)silyl]oxymethyl]-3-oxo-2-bicyclo[2.2.1]heptanylidene]acetate | 150423-44-2

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: methyl (2Z)-2-[(1R,4S,5R,6R)-5,6-bis[[tert-butyl(diphenyl)silyl]oxymethyl]-3-oxo-2-bicyclo[2.2.1]heptanylidene]acetate
• CAS: 150423-44-2
• 化学式: C₄₄H₅₂O₅Si₂
• 分子量: 717.065
• InChiKey: SQADZCPHJUOGGV-RZFUBBAPSA-N

物化性质

• 沸点：
  701.2±60.0 °C(predicted)
• 密度：
  1.13±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.69
• 重原子数：
  51
• 可旋转键数：
  14
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  61.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  methyl (2Z)-2-[(1R,4S,5R,6R)-5,6-bis[[tert-butyl(diphenyl)silyl]oxymethyl]-3-oxo-2-bicyclo[2.2.1]heptanylidene]acetate 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 生成
  参考文献：
  名称：

  Differentiation of enantiotopic carbonyl groups by the horner-wadsworth-emmons reaction

  摘要：

  A chiral phosphonoacetate 2 differentiates the enantiotopic carbonyl groups in an alpha-diketone 5 to afford the Z-olefin 6 in high yield and ee. The absolute stereochemistry of 6 was determined by X-ray analysis of 8 derived from 6.

  DOI：

  10.1016/s0040-4039(00)60618-4
• 作为产物：
  描述：

  甲醇 、 [1-(2-hydroxynaphthalen-1-yl)naphthalen-2-yl] (2Z)-2-[(1R,4S,5R,6R)-5,6-bis[[tert-butyl(diphenyl)silyl]oxymethyl]-3-oxo-2-bicyclo[2.2.1]heptanylidene]acetate 在 sodium hydride 作用下， 反应 1.0h， 生成 、 methyl (2Z)-2-[(1R,4S,5R,6R)-5,6-bis[[tert-butyl(diphenyl)silyl]oxymethyl]-3-oxo-2-bicyclo[2.2.1]heptanylidene]acetate
  参考文献：
  名称：

  用手性联萘酯的霍纳-沃兹沃思-埃蒙斯试剂区分内消旋-α-二酮的羰基

  摘要：

  考察了选定的内消旋-α-二羰基化合物与手性膦酸酯试剂的非对称霍纳-沃兹沃思-埃蒙斯反应，该手性膦酸酯试剂在羧酸盐部分具有轴向不对称的1,1'-bi-2-或8-萘酚作为手性助剂。反应顺利进行，化学收率高，非对映选择性高。Z-烯烃优先形成，并且发现萘环上2'-或8'-位的游离羟基在高非对映选择性中起着至关重要的作用，这可能是由于络合物诱导的邻近效应所致。还介绍了机械方面的考虑。

  DOI：

  10.1016/j.tet.2007.10.006

文献信息

• Formation of non-racemic E- and Z-olefins based on discrimination of enantiotopic carbonyl groups in α-diketones by a chiral phosphonate reagent
  作者：Kiyoshi Tanaka、Toshiyuki Watanabe、Yoshihisa Ohta、Kaoru Fuji

  DOI：10.1016/s0040-4039(97)10328-8

  日期：1997.12

  A chiral HWE reagent reacted with an alternative carbonyl group of meso-alpha-diketones of bicyclo[2.2.1] system to give non-racemic (Z)- and (E)-olefins, respectively. (C) 1997 Elsevier Science Ltd.
• Discrimination of carbonyl groups of meso-α-diketones with Horner–Wadsworth–Emmons reagent of chiral binaphthyl esters
  作者：Daiki Monguchi、Yoshihisa Ohta、Tatsuya Yoshiuchi、Toshiyuki Watanabe、Takumi Furuta、Kiyoshi Tanaka、Kaoru Fuji

  DOI：10.1016/j.tet.2007.10.006

  日期：2007.12

  meso-α-dicarbonyl compounds with chiral phosphonate reagents, which possessed axially dissymmetric 1,1′-bi-2- or 8-naphthol at the carboxylate moiety as a chiral auxiliary, were examined. The reactions proceeded smoothly with good chemical yields as well as with high diastereoselectivities. Z-olefins were preferentially formed, and it was found that the free hydroxy group at the 2′- or 8′-position on the naphthalene

  考察了选定的内消旋-α-二羰基化合物与手性膦酸酯试剂的非对称霍纳-沃兹沃思-埃蒙斯反应，该手性膦酸酯试剂在羧酸盐部分具有轴向不对称的1,1'-bi-2-或8-萘酚作为手性助剂。反应顺利进行，化学收率高，非对映选择性高。Z-烯烃优先形成，并且发现萘环上2'-或8'-位的游离羟基在高非对映选择性中起着至关重要的作用，这可能是由于络合物诱导的邻近效应所致。还介绍了机械方面的考虑。
• Differentiation of enantiotopic carbonyl groups by the horner-wadsworth-emmons reaction
  作者：Kiyoshi Tanaka、Yoshihisa Ohta、Kaoru Fuji、Tooru Taga

  DOI：10.1016/s0040-4039(00)60618-4

  日期：1993.6

  A chiral phosphonoacetate 2 differentiates the enantiotopic carbonyl groups in an alpha-diketone 5 to afford the Z-olefin 6 in high yield and ee. The absolute stereochemistry of 6 was determined by X-ray analysis of 8 derived from 6.