Ethyl (3'R^*,3'aR^*,7'aR^*)-Tetrahydro-7'a-(hydroxymethyl)spiro<1,3-dioxolane-2,4'(3'aH)-indan>-3'-acetate | 139017-49-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: Ethyl (3'R^*,3'aR^*,7'aR^*)-Tetrahydro-7'a-(hydroxymethyl)spiro<1,3-dioxolane-2,4'(3'aH)-indan>-3'-acetate
• 英文别名: Ethyl (3'R^*,3'aR^*,7'aR^*)-Tetrahydro-7'a-(hydroxymethyl)spiro[1,3-dioxolane-2,4'(3'aH)-indan]-3'-acetate；ethyl 2-[(1'R,3'aR,7'aR)-3'a-(hydroxymethyl)spiro[1,3-dioxolane-2,7'-2,3,4,5,6,7a-hexahydro-1H-indene]-1'-yl]acetate
• CAS: 139017-49-5
• 化学式: C₁₆H₂₆O₅
• 分子量: 298.379
• InChiKey: FZXFWTXMEGEYHJ-YUELXQCFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.87
• 重原子数：
  21.0
• 可旋转键数：
  4.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.94
• 拓扑面积：
  64.99
• 氢给体数：
  1.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  Ethyl (3'R^*,3'aR^*,7'aR^*)-Tetrahydro-7'a-(hydroxymethyl)spiro<1,3-dioxolane-2,4'(3'aH)-indan>-3'-acetate 在 甲酸 、 偶氮二异丁腈 、 四溴化碳 、 potassium tert-butylate 、 水 、 三正丁基氢锡 、 三苯基膦 作用下， 以 苯 为溶剂， 反应 32.5h， 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
• 作为产物：
  描述：

  (1R,5R,8S)-1-But-3-enyl-8-iodo-5-methoxy-6-oxa-bicyclo[3.2.1]oct-2-en-7-one 在 palladium on activated charcoal sodium tetrahydroborate 、 sodium periodate 、 四氧化锇 、 草酰氯 、 偶氮二异丁腈 、 氢气 、 三正丁基氢锡 、 对甲苯磺酸 、 原甲酸三甲酯 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 、 叔丁醇 、 苯 为溶剂， 反应 3.17h， 生成 Ethyl (3'R^*,3'aR^*,7'aR^*)-Tetrahydro-7'a-(hydroxymethyl)spiro<1,3-dioxolane-2,4'(3'aH)-indan>-3'-acetate
  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