Ethyl (1R*,3aS*,7aR*)-α--hexahydro-3a-methyl-7-methylene-1-indanacetate | 139017-59-7

• 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: Ethyl (1R*,3aS*,7aR*)-α--hexahydro-3a-methyl-7-methylene-1-indanacetate
• 英文别名: Ethyl (1R^*,3aS^*,7aR^*)-α--hexahydro-3a-methyl-7-methylene-1-indanacetate；Ethyl (1R^*,3aS^*,7aR^*)-α-[Bis(methylthio)methylene]-hexahydro-3a-methyl-7-methylene-1-indanacetate
• CAS: 139017-59-7
• 化学式: C₁₈H₂₈O₂S₂
• 分子量: 340.551
• InChiKey: DJOZXLJTRWWXIS-DHSIGJKJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.26
• 重原子数：
  22.0
• 可旋转键数：
  5.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.72
• 拓扑面积：
  26.3
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  甲基锂 、 Ethyl (1R*,3aS*,7aR*)-α--hexahydro-3a-methyl-7-methylene-1-indanacetate 在 copper(I) bromide dimethylsulfide complex 作用下， 生成 Ethyl (1R*,3aR*,7aS*)-Hexahydro-α-isopropylidene-3a-methyl-7-methylene-1-indanacetate 、 (Z)-2-((1R,3aR,7aR)-3a-Methyl-7-methylene-octahydro-inden-1-yl)-3-methylsulfanyl-acrylic acid ethyl ester
  参考文献：
  名称：

  Synthetic approaches to the axane family of sesquiterpenoids. Total synthesis of (dl)-axamide-4, (dl)-axisonitrile-4, and (dl)-axisothiocyanate-4

  摘要：

  Two methods for the preparation of perhydroindan 7 are described. One involves an intramolecular free radical cyclization in a key step and proceeds in 13 steps and 9% yield from anisole (9). The other involves an intramolecular conjugate addition mediated by pyrrolidine (28 --> 7) and proceeds in five steps and 30% overall yield from vinylogous ester 29. Two unsuccessful attempts to convert 7 into axane sesquiterpenoids 1-6 are described. The synthesis of axanes 4-6 was achieved using a potassium tert-butoxide catalyzed cyclization of a dienoic keto ester as a key step (47 + 48 --> 49). Conversion of alpha,beta-unsaturated ester 49 to vinyl isocyanate 57 was accomplished using a Curtius rearrangement and reduction of 57 with lithium triethylborohydride completed the synthesis of axamide-4 (4). The preparation of axisonitrile-4 (5) and axisothiocyanate-4 (6) from 4 is also described.

  DOI：

  10.1021/jo00033a023
• 作为产物：
  描述：

  3-((1R,5R,8S)-8-Iodo-5-methoxy-7-oxo-6-oxa-bicyclo[3.2.1]oct-2-en-1-yl)-propionaldehyde 在 palladium on activated charcoal sodium tetrahydroborate 、 甲酸 、 草酰氯 、 偶氮二异丁腈 、 四溴化碳 、 potassium tert-butylate 、 水 、 氢气 、 三正丁基氢锡 、 对甲苯磺酸 、 三苯基膦 、 原甲酸三甲酯 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 苯 为溶剂， 反应 35.67h， 生成 Ethyl (1R*,3aS*,7aR*)-α--hexahydro-3a-methyl-7-methylene-1-indanacetate
  参考文献：
  名称：

  Synthetic approaches to the axane family of sesquiterpenoids. Total synthesis of (dl)-axamide-4, (dl)-axisonitrile-4, and (dl)-axisothiocyanate-4

  摘要：

  Two methods for the preparation of perhydroindan 7 are described. One involves an intramolecular free radical cyclization in a key step and proceeds in 13 steps and 9% yield from anisole (9). The other involves an intramolecular conjugate addition mediated by pyrrolidine (28 --> 7) and proceeds in five steps and 30% overall yield from vinylogous ester 29. Two unsuccessful attempts to convert 7 into axane sesquiterpenoids 1-6 are described. The synthesis of axanes 4-6 was achieved using a potassium tert-butoxide catalyzed cyclization of a dienoic keto ester as a key step (47 + 48 --> 49). Conversion of alpha,beta-unsaturated ester 49 to vinyl isocyanate 57 was accomplished using a Curtius rearrangement and reduction of 57 with lithium triethylborohydride completed the synthesis of axamide-4 (4). The preparation of axisonitrile-4 (5) and axisothiocyanate-4 (6) from 4 is also described.

  DOI：

  10.1021/jo00033a023