(+)-aphanamol I | 91410-61-6

• 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: (+)-aphanamol I
• 英文别名: Aphanamol I；(1S,3aR,8aR)-7-(hydroxymethyl)-3a-methyl-1-propan-2-yl-1,2,3,5,6,8a-hexahydroazulen-4-one
• CAS: 91410-61-6
• 化学式: C₁₅H₂₄O₂
• 分子量: 236.354
• InChiKey: GOLVWBBRGXFBMA-KCQAQPDRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (+)-aphanamol I 在 sodium tetrahydroborate 作用下， 以 乙醇 为溶剂， 反应 0.75h， 以60%的产率得到(1R,2S,7R,8S)-isodauc-5-ene-2,12-diol
  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：

  (2R,3S)-2-[(R)-Acetoxy-(1-benzyloxymethyl-cyclopropyl)-methyl]-3-isopropyl-6,8-dimethyl-nona-6,7-dienoic acid methyl ester 在 di(rhodium)tetracarbonyl dichloride sodium tetrahydroborate 、 cerium(III) chloride 、 二甲基硫 、 氰化钠 、 臭氧 、 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 甲醇 、 二氯甲烷 、 水 、 二甲基亚砜 、 甲苯 为溶剂， 反应 151.5h， 生成 (+)-aphanamol I
  参考文献：
  名称：

  基于过渡金属催化的[5 + 2]丙二烯和乙烯基环丙烷的环加成反应，不对称合成（+）-AphanamolI。

  摘要：

  基于过渡金属催化的[5 + 2]烯基-乙烯基环丙烷环加成反应，简明地描述了（+）-Aphanamol I的简明不对称全合成。关键的环加成前体通过新的脱羧脱水反应由（R）-（+）-柠檬烯和环丙烷二酯聚合组装。该前体的金属催化[5 + 2]环加成反应具有完全的化学，内/外和非对映选择性，产率93％，代表了通向双环[5.3.0]癸烷衍生物的有效一般路线。

  DOI：

  10.1021/ol006085q

文献信息

• A Short Synthesis of Aphanamol I in Both Racemic and Enantiopure Forms
  作者：Steven J. Ferrara、Jonathan W. Burton

  DOI：10.1002/chem.201602669

  日期：2016.8.8

  A short synthesis of the biologically active sesquiterpene natural product (+)‐aphanamol I in both racemic and enantiopure forms is reported. Key steps include: a catalytic enantioselective conjugate addition, an oxidative radical cyclization, and a ring‐expanding Claisen rearrangement.

  报道了外消旋和对映体纯形式的生物活性倍半萜天然产物 (+)-aphanamol I 的简短合成。关键步骤包括：催化对映选择性共轭加成、氧化自由基环化和扩环克莱森重排。
• Asymmetric Total Synthesis of (+)-Aphanamol I Based on the Transition Metal Catalyzed [5 + 2] Cycloaddition of Allenes and Vinylcyclopropanes
  作者：Paul A. Wender、Lei Zhang

  DOI：10.1021/ol006085q

  日期：2000.7.1

  A concise asymmetric total synthesis of (+)-aphanamol I is described, based on the transition metal catalyzed [5 + 2] allenyl-vinylcyclopropane cycloaddition. The key cycloaddition precursor is convergently assembled from (R)-(+)-limonene and cyclopropane diester through a novel decarboxylative dehydration reaction. The metal-catalyzed [5 + 2] cycloaddition of this precursor proceeds with complete

  基于过渡金属催化的[5 + 2]烯基-乙烯基环丙烷环加成反应，简明地描述了（+）-Aphanamol I的简明不对称全合成。关键的环加成前体通过新的脱羧脱水反应由（R）-（+）-柠檬烯和环丙烷二酯聚合组装。该前体的金属催化[5 + 2]环加成反应具有完全的化学，内/外和非对映选择性，产率93％，代表了通向双环[5.3.0]癸烷衍生物的有效一般路线。
• 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.