(1S^*,5R^*)-N-<5-(benzyloxy)-2-(3,4-dimethoxyphenyl)cyclohex-2-en-1-yl>-α,α-dichloro-N-methylacetamide | 125032-08-8

• 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: (1S^*,5R^*)-N-<5-(benzyloxy)-2-(3,4-dimethoxyphenyl)cyclohex-2-en-1-yl>-α,α-dichloro-N-methylacetamide
• 英文别名: (1S^*,5R^*)-N-[5-(benzyloxy)-2-(3,4-dimethoxyphenyl)cyclohex-2-en-1-yl]-α,α-dichloro-N-methylacetamide；2,2-dichloro-N-[(1S,5R)-2-(3,4-dimethoxyphenyl)-5-phenylmethoxycyclohex-2-en-1-yl]-N-methylacetamide
• CAS: 125032-08-8
• 化学式: C₂₄H₂₇Cl₂NO₄
• 分子量: 464.389
• InChiKey: DMGYSRZUSWAAQG-QUCCMNQESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  31
• 可旋转键数：
  8
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  48
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (1S^*,5R^*)-N-<5-(benzyloxy)-2-(3,4-dimethoxyphenyl)cyclohex-2-en-1-yl>-α,α-dichloro-N-methylacetamide 在 palladium on activated charcoal 盐酸 、 sodium tetrahydroborate 、 jones reagent 、 硼烷四氢呋喃络合物 、 偶氮二异丁腈 、 氢气 、 三正丁基氢锡 作用下， 以 四氢呋喃 、 甲醇 、 乙醇 、 丙酮 、 甲苯 为溶剂， 25.0 ℃ 、392.24 kPa 条件下， 反应 26.17h， 生成 (+/-)-6-epimesembranol
  参考文献：
  名称：

  Radical cyclization of N-(cyclohex-2-enyl)-.alpha.,.alpha.-dichloroacetamides. Stereoselective syntheses of (.+-.)-mesembranol and (.+-.)-elwesine

  摘要：

  Stereoselective syntheses of the Sceletium alkaloid (+/-)-mesembranol (2) and the Amaryllidaceae alkaloid (+/-)-elwesine (3) have been achieved. A key step in the syntheses involves the Bu3SnH-mediated radical cyclization of the dichloroacetamides 34 and 46, which provides the cis-3a-aryloctahydroindolones 36 and 47, respectively. The amides 34 and 46 were prepared in a highly stereocontrolled manner from the corresponding 1-arylcyclohexenes 29 and 41 along the lines: 29 --> 30a --> 31 --> 32 --> 33 --> 34 and 41 --> 42a --> 44a --> 45a --> 46. Transformation of 36 into (+/-)-mesembranol was readily accomplished by reduction with diborane and subsequent removal of the O-benzyl protecting group by hydrogenolysis over Pd/C. On the other hand, debenzylation of 36 with Raney Ni afforded a mixture of the 6-alpha- and 6-beta-alcohols 39a and 39b, which was then reduced by alane to give a separable mixture of (+/-)-mesembranol and (+/-)-6-epimesembranol (40). Reduction of 47 with diborane followed by catalytic hydrogenolysis over Pd/C afforded the amino alcohol 50, which has already been converted into (+/-)-elwesine by Pictet-Spengler cyclization.

  DOI：

  10.1021/jo00001a021
• 作为产物：
  描述：

  4-溴黎芦醚 在 N-溴代丁二酰亚胺(NBS) 、 水 、 对甲苯磺酸 、 三乙胺 作用下， 以 甲醇 、 二氯甲烷 、 乙腈 、 苯 为溶剂， 反应 10.0h， 生成 (1S^*,5R^*)-N-<5-(benzyloxy)-2-(3,4-dimethoxyphenyl)cyclohex-2-en-1-yl>-α,α-dichloro-N-methylacetamide
  参考文献：
  名称：

  Radical cyclization of N-(cyclohex-2-enyl)-.alpha.,.alpha.-dichloroacetamides. Stereoselective syntheses of (.+-.)-mesembranol and (.+-.)-elwesine

  摘要：

  Stereoselective syntheses of the Sceletium alkaloid (+/-)-mesembranol (2) and the Amaryllidaceae alkaloid (+/-)-elwesine (3) have been achieved. A key step in the syntheses involves the Bu3SnH-mediated radical cyclization of the dichloroacetamides 34 and 46, which provides the cis-3a-aryloctahydroindolones 36 and 47, respectively. The amides 34 and 46 were prepared in a highly stereocontrolled manner from the corresponding 1-arylcyclohexenes 29 and 41 along the lines: 29 --> 30a --> 31 --> 32 --> 33 --> 34 and 41 --> 42a --> 44a --> 45a --> 46. Transformation of 36 into (+/-)-mesembranol was readily accomplished by reduction with diborane and subsequent removal of the O-benzyl protecting group by hydrogenolysis over Pd/C. On the other hand, debenzylation of 36 with Raney Ni afforded a mixture of the 6-alpha- and 6-beta-alcohols 39a and 39b, which was then reduced by alane to give a separable mixture of (+/-)-mesembranol and (+/-)-6-epimesembranol (40). Reduction of 47 with diborane followed by catalytic hydrogenolysis over Pd/C afforded the amino alcohol 50, which has already been converted into (+/-)-elwesine by Pictet-Spengler cyclization.

  DOI：

  10.1021/jo00001a021

文献信息

• Synthesis of (±)-mesembranol by radical cyclisation of α,α-dichloroacetamides
  作者：Hiroyuki Ishibashi、Taru Su So、Tatsunori Sato、Katsuko Kuroda、Masazumi Ikeda

  DOI：10.1039/c39890000762

  日期：——

  (±)-Mesembranol was synthesised in a highly stereoselective manner using Bu3SnH mediated radical cyclisation of α,α-dichloroacetamide as the key step.

  以Bu 3 SnH介导的α，α-二氯乙酰胺自由基环化为关键步骤，以高度立体选择性的方式合成了（±）-Mesembranol 。
• Radical cyclization of N-(cyclohex-2-enyl)-.alpha.,.alpha.-dichloroacetamides. Stereoselective syntheses of (.+-.)-mesembranol and (.+-.)-elwesine
  作者：Hiroyuki Ishibashi、Taru Su So、Kyoko Okochi、Tatsunori Sato、Nobuyuki Nakamura、Hiroshi Nakatani、Masazumi Ikeda

  DOI：10.1021/jo00001a021

  日期：1991.1

  Stereoselective syntheses of the Sceletium alkaloid (+/-)-mesembranol (2) and the Amaryllidaceae alkaloid (+/-)-elwesine (3) have been achieved. A key step in the syntheses involves the Bu3SnH-mediated radical cyclization of the dichloroacetamides 34 and 46, which provides the cis-3a-aryloctahydroindolones 36 and 47, respectively. The amides 34 and 46 were prepared in a highly stereocontrolled manner from the corresponding 1-arylcyclohexenes 29 and 41 along the lines: 29 --> 30a --> 31 --> 32 --> 33 --> 34 and 41 --> 42a --> 44a --> 45a --> 46. Transformation of 36 into (+/-)-mesembranol was readily accomplished by reduction with diborane and subsequent removal of the O-benzyl protecting group by hydrogenolysis over Pd/C. On the other hand, debenzylation of 36 with Raney Ni afforded a mixture of the 6-alpha- and 6-beta-alcohols 39a and 39b, which was then reduced by alane to give a separable mixture of (+/-)-mesembranol and (+/-)-6-epimesembranol (40). Reduction of 47 with diborane followed by catalytic hydrogenolysis over Pd/C afforded the amino alcohol 50, which has already been converted into (+/-)-elwesine by Pictet-Spengler cyclization.