(+)-(5S,6aS,9aR,9bS)-9,9-(2,2-Dimethylpropylenedioxy)-6a-(3,4-dimethoxyphenyl)-5-{[(1R,2S)-2-(1-methyl-1-phenylethyl)cyclohexyl]oxy}hexahydro-1H-isooxazolo-[2,3,3-h] [2,1]benzoxazine | 187850-39-1

• 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: (+)-(5S,6aS,9aR,9bS)-9,9-(2,2-Dimethylpropylenedioxy)-6a-(3,4-dimethoxyphenyl)-5-{[(1R,2S)-2-(1-methyl-1-phenylethyl)cyclohexyl]oxy}hexahydro-1H-isooxazolo-[2,3,3-h] [2,1]benzoxazine
• 英文别名: (4'R,8'S,10'S,12'S)-8'-(3,4-dimethoxyphenyl)-5,5-dimethyl-10'-[(1R,2S)-2-(2-phenylpropan-2-yl)cyclohexyl]oxyspiro[1,3-dioxane-2,5'-2,11-dioxa-1-azatricyclo[6.3.1.04,12]dodecane]
• CAS: 187850-39-1
• 化学式: C₃₇H₅₁NO₇
• 分子量: 621.814
• InChiKey: JJDSNBNUKDHUNN-KSTLRHSPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8
• 重原子数：
  45
• 可旋转键数：
  7
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.68
• 拓扑面积：
  67.8
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  (+)-(5S,6aS,9aR,9bS)-9,9-(2,2-Dimethylpropylenedioxy)-6a-(3,4-dimethoxyphenyl)-5-{[(1R,2S)-2-(1-methyl-1-phenylethyl)cyclohexyl]oxy}hexahydro-1H-isooxazolo-[2,3,3-h] [2,1]benzoxazine 在 镍 sodium hydroxide 、 乙基溴化镁 、 氢气 、 三氟乙酸 、 1,1'-azodicarbonyl-dipiperidine 、 叔丁醇 作用下， 以 甲醇 为溶剂， 25.0 ℃ 、2.07 MPa 条件下， 反应 129.33h， 生成 松叶菊碱提取物
  参考文献：
  名称：

  Asymmetric Construction of a Quaternary Carbon Center by Tandem [4 + 2]/[3 + 2] Cycloaddition of a Nitroalkene. The Total Synthesis of (−)-Mesembrine

  摘要：

  An efficient, total synthesis of the Sceletium alkaloid (-)-mesembrine is accomplished in seven steps and 19% yield from a functionalized nitroalkene (itself prepared in six steps and 34% yield from ethyl 3-bromopropionate). The construction of the octahydroindole framework of mesembrine features a tandem inter [4 + 2]/intra [3 + 2] cycloaddition of a 2,2-disubstituted 1-nitroalkene and a chiral vinyl ether derived from (1R,2S)-2-(l-methyl-l-phenylethyl)cyclo as the central strategic element. The two stereogenic centers of the natural product, which include a benzylic, quaternary center, were established in 26/1 selectivity in the tandem process.

  DOI：

  10.1021/jo970079z
• 作为产物：
  描述：

  1,5-二溴-3-戊酮 在 2,6-二叔丁基-4-甲基苯酚 、 双氧水 、 三甲基铝 、 对甲苯磺酸 、 sodium iodide 作用下， 以 四氢呋喃 、 二氯甲烷 、 丙酮 、 甲苯 、 苯 为溶剂， 反应 149.5h， 生成 (+)-(5S,6aS,9aR,9bS)-9,9-(2,2-Dimethylpropylenedioxy)-6a-(3,4-dimethoxyphenyl)-5-{[(1R,2S)-2-(1-methyl-1-phenylethyl)cyclohexyl]oxy}hexahydro-1H-isooxazolo-[2,3,3-h] [2,1]benzoxazine
  参考文献：
  名称：

  Asymmetric Construction of a Quaternary Carbon Center by Tandem [4 + 2]/[3 + 2] Cycloaddition of a Nitroalkene. The Total Synthesis of (−)-Mesembrine

  摘要：

  An efficient, total synthesis of the Sceletium alkaloid (-)-mesembrine is accomplished in seven steps and 19% yield from a functionalized nitroalkene (itself prepared in six steps and 34% yield from ethyl 3-bromopropionate). The construction of the octahydroindole framework of mesembrine features a tandem inter [4 + 2]/intra [3 + 2] cycloaddition of a 2,2-disubstituted 1-nitroalkene and a chiral vinyl ether derived from (1R,2S)-2-(l-methyl-l-phenylethyl)cyclo as the central strategic element. The two stereogenic centers of the natural product, which include a benzylic, quaternary center, were established in 26/1 selectivity in the tandem process.

  DOI：

  10.1021/jo970079z

文献信息

• Asymmetric Construction of a Quaternary Carbon Center by Tandem [4 + 2]/[3 + 2] Cycloaddition of a Nitroalkene. The Total Synthesis of (−)-Mesembrine
  作者：Scott E. Denmark、Lawrence R. Marcin

  DOI：10.1021/jo970079z

  日期：1997.3.1

  An efficient, total synthesis of the Sceletium alkaloid (-)-mesembrine is accomplished in seven steps and 19% yield from a functionalized nitroalkene (itself prepared in six steps and 34% yield from ethyl 3-bromopropionate). The construction of the octahydroindole framework of mesembrine features a tandem inter [4 + 2]/intra [3 + 2] cycloaddition of a 2,2-disubstituted 1-nitroalkene and a chiral vinyl ether derived from (1R,2S)-2-(l-methyl-l-phenylethyl)cyclo as the central strategic element. The two stereogenic centers of the natural product, which include a benzylic, quaternary center, were established in 26/1 selectivity in the tandem process.