1,1-Dimethylethyl (1R^*,3aR^*,7aS^*)-Hexahydro-α-isopropylidene-3a-methyl-7-oxo-1-indanacetate | 127488-37-3

• 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: 1,1-Dimethylethyl (1R^*,3aR^*,7aS^*)-Hexahydro-α-isopropylidene-3a-methyl-7-oxo-1-indanacetate
• 英文别名: tert-butyl 2-[(1R,3aR,7aS)-3a-methyl-7-oxo-2,3,4,5,6,7a-hexahydro-1H-inden-1-yl]-3-methylbut-2-enoate
• CAS: 127488-37-3
• 化学式: C₁₉H₃₀O₃
• 分子量: 306.445
• InChiKey: FFKZNLDDOSKSFO-URKNILKWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  22
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.79
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1,1-Dimethylethyl (1R^*,3aR^*,7aS^*)-Hexahydro-α-isopropylidene-3a-methyl-7-oxo-1-indanacetate 在 palladium on activated charcoal lithium aluminium tetrahydride 、 jones reagent 、 potassium tert-butylate 、 氢气 作用下， 以 乙醚 、 乙酸乙酯 、 丙酮 、 叔丁醇 为溶剂， 25.0 ℃ 、275.79 kPa 条件下， 反应 65.0h， 生成 (αR^*,1R^*,3aR^*,7aS^*)-Hexahydro-α-isopropyl-3a-methyl-7-methylene-1-indanacetic acid
  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-乙氧基-2-环己烯-1-酮 在 四氢吡咯 、 盐酸 、 二甲基硫 、 对甲苯磺酸 、 臭氧 、 溶剂黄146 、 copper(I) bromide 、 lithium diisopropyl amide 、 原甲酸三甲酯 作用下， 以 四氢呋喃 、 苯 为溶剂， 反应 42.75h， 生成 1,1-Dimethylethyl (1R^*,3aR^*,7aS^*)-Hexahydro-α-isopropylidene-3a-methyl-7-oxo-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

文献信息

• HART, DAVID J.;LAI, CHIN-SHAN, SYNLETT.,(1989) N, C. 49-51
  作者：HART, DAVID J.、LAI, CHIN-SHAN

  DOI：——

  日期：——
• Synthetic approaches to the axane family of sesquiterpenoids. Total synthesis of (dl)-axamide-4, (dl)-axisonitrile-4, and (dl)-axisothiocyanate-4
  作者：Balan Chenera、Che Ping Chuang、David J. Hart、Chin Shan Lai

  DOI：10.1021/jo00033a023

  日期：1992.3

  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.