(1R,2R,3R,6S,7R,10S)-10-isopropyl-7-methyltricyclo<5.3.0.0^2,6>decane-3-spiro-2'-oxiran-6-yl benzoate | 142896-02-4

• 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: (1R,2R,3R,6S,7R,10S)-10-isopropyl-7-methyltricyclo<5.3.0.0^2,6>decane-3-spiro-2'-oxiran-6-yl benzoate
• 英文别名: [(1'S,2S,2'R,5'S,6'R,7'R)-2'-methyl-5'-propan-2-ylspiro[oxirane-2,8'-tricyclo[5.3.0.02,6]decane]-1'-yl] benzoate
• CAS: 142896-02-4
• 化学式: C₂₂H₂₈O₃
• 分子量: 340.463
• InChiKey: CYIXMYYUXQSZJI-DZKVBSAQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.9
• 重原子数：
  25
• 可旋转键数：
  4
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.68
• 拓扑面积：
  38.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (1R,2R,3R,6S,7R,10S)-10-isopropyl-7-methyltricyclo<5.3.0.0^2,6>decane-3-spiro-2'-oxiran-6-yl benzoate 在 氢氧化钾 作用下， 以 甲醇 为溶剂， 反应 2.0h， 以32%的产率得到(+)-aphanamol I
  参考文献：
  名称：

  A short enantiospecific route to isodaucane sesquiterpenes from limonene. On the absolute configuration of (+)-aphanamol I and II.

  摘要：

  The isodaucane sesquiterpenes (+)-aphanamol I (3) and (-)-2-oxoisodauc-5-en-12-al [(-)-6] have been prepared in a short reaction sequence from 5(S)-isopropyl-2-methyl-l-cyclopentene-1-carbaldehyde (S)-23 (readily obtainable from (+)-limonene). Key steps were a de Mayo type photocyclization of an 3-acyloxy-2-cyclopenten-1-one with 3(S)-isopropyl-1-methylcyclopentene [(S)-24] to a [5.3.0.0(2.6)]tricyclodecanone (e.g., (-)-28) with the desired configuration at all stereocenters and the formation of 3 by a base-catalyzed fragmentation of the gamma,delta-epoxyalcohol intermediate 33 (R = H), which produced all the desired functional groups in one step. The stereochemical assignments were supported by CD data as well as by the synthesis of (-)-norbourbonone (29) from (S)-24, which is a novel chiral intermediate. These results are in confliction with some earlier assignmnents of the absolute configuration in the isodaucane group of sesquiterpenes.

  DOI：

  10.1021/jo00046a018
• 作为产物：
  描述：

  (1R,2R,6S,7R,10S)-6-(benzoyloxy)-10-isopropyl-7-methyltricyclo<5.3.0.0^2,6>-3-decanone 、 dimethylsulfoxonium methylide 以 四氢呋喃 为溶剂， 反应 3.5h， 以68%的产率得到(1R,2R,3R,6S,7R,10S)-10-isopropyl-7-methyltricyclo<5.3.0.0^2,6>decane-3-spiro-2'-oxiran-6-yl benzoate
  参考文献：
  名称：

  A short enantiospecific route to isodaucane sesquiterpenes from limonene. On the absolute configuration of (+)-aphanamol I and II.

  摘要：

  The isodaucane sesquiterpenes (+)-aphanamol I (3) and (-)-2-oxoisodauc-5-en-12-al [(-)-6] have been prepared in a short reaction sequence from 5(S)-isopropyl-2-methyl-l-cyclopentene-1-carbaldehyde (S)-23 (readily obtainable from (+)-limonene). Key steps were a de Mayo type photocyclization of an 3-acyloxy-2-cyclopenten-1-one with 3(S)-isopropyl-1-methylcyclopentene [(S)-24] to a [5.3.0.0(2.6)]tricyclodecanone (e.g., (-)-28) with the desired configuration at all stereocenters and the formation of 3 by a base-catalyzed fragmentation of the gamma,delta-epoxyalcohol intermediate 33 (R = H), which produced all the desired functional groups in one step. The stereochemical assignments were supported by CD data as well as by the synthesis of (-)-norbourbonone (29) from (S)-24, which is a novel chiral intermediate. These results are in confliction with some earlier assignmnents of the absolute configuration in the isodaucane group of sesquiterpenes.

  DOI：

  10.1021/jo00046a018

文献信息

• A short enantiospecific route to isodaucane sesquiterpenes from limonene. On the absolute configuration of (+)-aphanamol I and II.
  作者：Thomas Hansson、Boerje Wickberg

  DOI：10.1021/jo00046a018

  日期：1992.9

  The isodaucane sesquiterpenes (+)-aphanamol I (3) and (-)-2-oxoisodauc-5-en-12-al [(-)-6] have been prepared in a short reaction sequence from 5(S)-isopropyl-2-methyl-l-cyclopentene-1-carbaldehyde (S)-23 (readily obtainable from (+)-limonene). Key steps were a de Mayo type photocyclization of an 3-acyloxy-2-cyclopenten-1-one with 3(S)-isopropyl-1-methylcyclopentene [(S)-24] to a [5.3.0.0(2.6)]tricyclodecanone (e.g., (-)-28) with the desired configuration at all stereocenters and the formation of 3 by a base-catalyzed fragmentation of the gamma,delta-epoxyalcohol intermediate 33 (R = H), which produced all the desired functional groups in one step. The stereochemical assignments were supported by CD data as well as by the synthesis of (-)-norbourbonone (29) from (S)-24, which is a novel chiral intermediate. These results are in confliction with some earlier assignmnents of the absolute configuration in the isodaucane group of sesquiterpenes.