(R,Z)-5-{3-[2-benzyloxy-4-(tert-butyldiphenylsilyloxy)phenyl]-1-(2-methoxyethoxy)methoxy-2-propen-2-yl}-2-methylcyclohex-2-en-1-one | 948582-58-9

• 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: (R,Z)-5-{3-[2-benzyloxy-4-(tert-butyldiphenylsilyloxy)phenyl]-1-(2-methoxyethoxy)methoxy-2-propen-2-yl}-2-methylcyclohex-2-en-1-one
• 英文别名: (5R)-5-[(Z)-1-[4-[tert-butyl(diphenyl)silyl]oxy-2-phenylmethoxyphenyl]-3-(2-methoxyethoxymethoxy)prop-1-en-2-yl]-2-methylcyclohex-2-en-1-one
• CAS: 948582-58-9
• 化学式: C₄₃H₅₀O₆Si
• 分子量: 690.952
• InChiKey: PUEHPGGEQRBBMR-CRAFIFAXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.15
• 重原子数：
  50
• 可旋转键数：
  17
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  63.2
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (R,Z)-5-{3-[2-benzyloxy-4-(tert-butyldiphenylsilyloxy)phenyl]-1-(2-methoxyethoxy)methoxy-2-propen-2-yl}-2-methylcyclohex-2-en-1-one 在 过氧化氢异丙苯 、 苄基三甲基氢氧化铵 作用下， 以 甲醇 、 甲苯 为溶剂， 反应 48.0h， 以87%的产率得到(2R,3R,5R,Z)-5-{3-[2-benzyloxy-4-(tert-butyldiphenylsilanyloxy)phenyl]-1-[(2-methoxyethoxy)methoxy]-2-propen-2-yl}-2,3-epoxy-2-methylcyclohexanone
  参考文献：
  名称：

  Synthetic studies toward miroestrols: trials for elongation of the methyl group of 5-substituted 2-methyl-2-cyclohexanone to 3-methyl-2-butenyl function

  摘要：

  Toward total synthesis of miroestrols (miroestrol and deoxymiroestrol), 3-methyl-2-butenyl function (endo-C5 unit) on D ring as a carbon chain for C and E rings was prepared by elongation of the methyl group in alpha-methyl-alpha.,beta-unsaturated ketone unit, and 3,5-dinitrobenzoyl group was introduced as a potential leaving group for the construction of B ring. The former was accomplished through a sequence of epoxide ring-opening, microwave-irradiated siloxy-Cope rearrangement, and isomerization of 3-methyl-3-butenyl function (exo-C5 unit) to endo-C5 unit. (C) 2008 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2008.11.055
• 作为产物：
  描述：

  (E)-(R)-5-{3-[2-benzyloxy-4-(tert-butyldiphenylsilyloxy)phenyl]-1-hydroxyprop-2-en-2-yl}-2-methylcyclohex-2-en-1-one 在 N,N-二异丙基乙胺 、 苯乙酮 作用下， 以 N,N-二甲基甲酰胺 、 苯 为溶剂， 反应 3.0h， 生成 (R,Z)-5-{3-[2-benzyloxy-4-(tert-butyldiphenylsilyloxy)phenyl]-1-(2-methoxyethoxy)methoxy-2-propen-2-yl}-2-methylcyclohex-2-en-1-one
  参考文献：
  名称：

  三氯化硼介导的间苯二酚衍生物的区域选择性克莱森重排：在间苯二酚香芹酚醚中的应用

  摘要：

  检测了间苯二酚烯丙基醚的克莱森重排 (CR)。尽管热 CR 的区域选择性较低，但在路易斯酸（如三氯化硼）存在下，选择性得到了很大改善。这种重排成功地应用于间苯二酚香芹酮醚，用于将香芹酮单元区域选择性地引入间苯二酚骨架，以合成植物雌激素微雌激素。

  DOI：

  10.1055/s-2007-983712

文献信息

• Synthetic studies toward miroestrols: trials for elongation of the methyl group of 5-substituted 2-methyl-2-cyclohexanone to 3-methyl-2-butenyl function
  作者：Fumihiro Ito、Takuya Kumamoto、Kentaro Yamaguchi、Tsutomu Ishikawa

  DOI：10.1016/j.tet.2008.11.055

  日期：2009.1

  Toward total synthesis of miroestrols (miroestrol and deoxymiroestrol), 3-methyl-2-butenyl function (endo-C5 unit) on D ring as a carbon chain for C and E rings was prepared by elongation of the methyl group in alpha-methyl-alpha.,beta-unsaturated ketone unit, and 3,5-dinitrobenzoyl group was introduced as a potential leaving group for the construction of B ring. The former was accomplished through a sequence of epoxide ring-opening, microwave-irradiated siloxy-Cope rearrangement, and isomerization of 3-methyl-3-butenyl function (exo-C5 unit) to endo-C5 unit. (C) 2008 Elsevier Ltd. All rights reserved.
• Boron Trichloride Mediated Regioselective Claisen Rearrangement of Resorcinol­ Derivatives: Application to Resorcinol Carvonyl Ethers
  作者：Takuya Kumamoto、Fumihiro Ito、Keiko Fusegi、Tsutomu Ishikawa

  DOI：10.1055/s-2007-983712

  日期：2007.6

  Claisen rearrangement (CR) of resorcinol allyl ethers was examined. Although thermal CR gave low regioselectivity, the selectivity was much improved in the presence of a Lewis acid such as boron trichloride. This rearrangement was successfully applied to resorcinol carvonyl ethers for the regioselective introduction of a carvone unit into the resorcinol skeleton for the synthesis of phytoestrogenic

  检测了间苯二酚烯丙基醚的克莱森重排 (CR)。尽管热 CR 的区域选择性较低，但在路易斯酸（如三氯化硼）存在下，选择性得到了很大改善。这种重排成功地应用于间苯二酚香芹酮醚，用于将香芹酮单元区域选择性地引入间苯二酚骨架，以合成植物雌激素微雌激素。