(1S,2R,3R,4S)-2-(1,4-Dioxaspiro<4.5>dec-6-en-6-yl)-3-(methoxymethoxy)-1-<(E)-2-(p-methoxyphenoxy)vinyl>-7,7-dimethyl-2-norbornanol | 162790-77-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: (1S,2R,3R,4S)-2-(1,4-Dioxaspiro<4.5>dec-6-en-6-yl)-3-(methoxymethoxy)-1-<(E)-2-(p-methoxyphenoxy)vinyl>-7,7-dimethyl-2-norbornanol
• 英文别名: (1S,2R,3R,4S)-2-(1,4-dioxaspiro[4.5]dec-6-en-6-yl)-3-(methoxymethoxy)-1-[(E)-2-(4-methoxyphenoxy)ethenyl]-7,7-dimethylbicyclo[2.2.1]heptan-2-ol
• CAS: 162790-77-4
• 化学式: C₂₈H₃₈O₇
• 分子量: 486.606
• InChiKey: ZBERSALRQKJGTH-VHULVHEHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  35
• 可旋转键数：
  8
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  75.6
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  (1S,2R,3R,4S)-2-(1,4-Dioxaspiro<4.5>dec-6-en-6-yl)-3-(methoxymethoxy)-1-<(E)-2-(p-methoxyphenoxy)vinyl>-7,7-dimethyl-2-norbornanol 在 水 、 4-甲基苯磺酸吡啶 作用下， 以 丙酮 为溶剂， 反应 0.5h， 以95%的产率得到2-<(1S,2R,3R,4S)-2-Hydroxy-3-(methoxymethoxy)-1-<(E)-2-(p-methoxyphenoxy)vinyl>-7,7-dimethyl-2-norbornyl>-2-cyclohexen-1-one
  参考文献：
  名称：

  Evaluation of 2-Bromocyclohexenone Acetals as Vehicles for the Introduction of C-7 Oxygen Preliminary to the Synthesis of Taxane Diterpenes

  摘要：

  The coupling of an optically pure, camphor-derived, beta,gamma-unsaturated, bicyclic ketone with a suitable vinyl organometallic is recognized to result in 1,2-addition from the endo face. Anionic oxy-Cope rearrangement of these carbinols proceeds via an ''endo-chair'' transition state to deliver a strained and reactive enolate that is formed regioselectively and is amenable to alpha-methylation from the top face. These steps, which are preliminary to a broad-based approach to the taxane diterpenes, had not yet accommodated suitable introduction of a C-7 oxygen substituent as required of taxol. Typically, an ether substituent at this site experiences beta-elimination once the enolate anion intermediate is accessed. Herein it is demonstrated that the parent 2-bromocyclohexenone acetal is well suited to resolving this complication. Halogen-metal exchange proceeds well to provide a suitably nucleophilic building block. Direct charge-accelerated sigmatropic rearrangement of the carbinol products does proceed with beta-elimination, but under the present circumstances the second C-O bond remains in the form of a vinylogous ester. Alternatively, the carbinols are amenable to chemoselective hydrolysis of the acetal, thereby unmasking a conjugated cyclohexenone part structure. These intermediates have been found to rearrange along completely analogous reaction trajectories to provide enolates of a beta-diketone subunit. The extent to which these anions undergo C- versus O-methylation under various conditions has been examined. When O-methylation does occur, it is the C-7 oxygen (and not the one at C-9) that is engaged in reaction.

  DOI：

  10.1021/jo00109a021
• 作为产物：
  描述：

  6-溴-1,4-二氧杂螺[4.5]癸-6-烯 、 (1S,3R,4S)-3-(Methoxymethoxy)-1-<(E)-2-(p-methoxyphenoxy)vinyl>-7,7-dimethyl-2-norbornanone 在 叔丁基锂 作用下， 以 四氢呋喃 、 正戊烷 为溶剂， 以64%的产率得到(1S,2R,3R,4S)-2-(1,4-Dioxaspiro<4.5>dec-6-en-6-yl)-3-(methoxymethoxy)-1-<(E)-2-(p-methoxyphenoxy)vinyl>-7,7-dimethyl-2-norbornanol
  参考文献：
  名称：

  Evaluation of 2-Bromocyclohexenone Acetals as Vehicles for the Introduction of C-7 Oxygen Preliminary to the Synthesis of Taxane Diterpenes

  摘要：

  The coupling of an optically pure, camphor-derived, beta,gamma-unsaturated, bicyclic ketone with a suitable vinyl organometallic is recognized to result in 1,2-addition from the endo face. Anionic oxy-Cope rearrangement of these carbinols proceeds via an ''endo-chair'' transition state to deliver a strained and reactive enolate that is formed regioselectively and is amenable to alpha-methylation from the top face. These steps, which are preliminary to a broad-based approach to the taxane diterpenes, had not yet accommodated suitable introduction of a C-7 oxygen substituent as required of taxol. Typically, an ether substituent at this site experiences beta-elimination once the enolate anion intermediate is accessed. Herein it is demonstrated that the parent 2-bromocyclohexenone acetal is well suited to resolving this complication. Halogen-metal exchange proceeds well to provide a suitably nucleophilic building block. Direct charge-accelerated sigmatropic rearrangement of the carbinol products does proceed with beta-elimination, but under the present circumstances the second C-O bond remains in the form of a vinylogous ester. Alternatively, the carbinols are amenable to chemoselective hydrolysis of the acetal, thereby unmasking a conjugated cyclohexenone part structure. These intermediates have been found to rearrange along completely analogous reaction trajectories to provide enolates of a beta-diketone subunit. The extent to which these anions undergo C- versus O-methylation under various conditions has been examined. When O-methylation does occur, it is the C-7 oxygen (and not the one at C-9) that is engaged in reaction.

  DOI：

  10.1021/jo00109a021