Toluene-4-sulfonic acid 2-((E)-(1S,2R,9R)-2-methoxymethoxy-15,15-dimethyl-3-oxo-tricyclo[10.2.1.0^4,9]pentadeca-4,11-dien-5-yloxy)-ethyl ester | 162790-82-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: Toluene-4-sulfonic acid 2-((E)-(1S,2R,9R)-2-methoxymethoxy-15,15-dimethyl-3-oxo-tricyclo[10.2.1.0^4,9]pentadeca-4,11-dien-5-yloxy)-ethyl ester
• 英文别名: 2-[[(1S,2R,9R,11E)-2-(methoxymethoxy)-15,15-dimethyl-3-oxo-5-tricyclo[10.2.1.04,9]pentadeca-4,11-dienyl]oxy]ethyl 4-methylbenzenesulfonate
• CAS: 162790-82-1
• 化学式: C₂₈H₃₈O₇S
• 分子量: 518.672
• InChiKey: XQEBLNXNVOCMCJ-UEMYFHTQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  36
• 可旋转键数：
  9
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.61
• 拓扑面积：
  96.5
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  Toluene-4-sulfonic acid 2-((E)-(1S,2R,9R)-2-methoxymethoxy-15,15-dimethyl-3-oxo-tricyclo[10.2.1.0^4,9]pentadeca-4,11-dien-5-yloxy)-ethyl ester 在 sodium iodide 作用下， 以 丙酮 为溶剂， 反应 3.5h， 以85%的产率得到(6R,7S,10E,12aR)-2,3,6,7,8,9,12,12a-Octahydro-6-hydroxy-4-(2-iodoethoxy)-13,13-dimethyl-7,10-methanobenzocyclodecen-5(1H)-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：

  对甲苯磺酰氯 、 (6R,7S,10E,12aR)-2,3,6,7,8,9,12,12a-Octahydro-4-(2-hydroxyethoxy)-6-(methoxymethoxy)-13,13-dimethyl-7,10-methanobenzocyclodecen-5(1H)-one 在 吡啶 作用下， 以95%的产率得到Toluene-4-sulfonic acid 2-((E)-(1S,2R,9R)-2-methoxymethoxy-15,15-dimethyl-3-oxo-tricyclo[10.2.1.0^4,9]pentadeca-4,11-dien-5-yloxy)-ethyl ester
  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