(2R,3R,5R)-2-[(2R,3aS,6aR)-hexahydrofuro[2,3-b]furan-2-yl]-5-isopropenyl-2,3-dimethylcyclohexane | 213833-81-9

• 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: (2R,3R,5R)-2-[(2R,3aS,6aR)-hexahydrofuro[2,3-b]furan-2-yl]-5-isopropenyl-2,3-dimethylcyclohexane
• 英文别名: (2R,3R,5R,2'R,3a'S,6a'R)-2-(hexahydrofuro[2,3-b]furan-2'-yl)-5-isopropenyl-2,3-dimethylcyclohexanone；(2R,3R,5R)-2-[(3aS,5R,6aR)-2,3,3a,4,5,6a-hexahydrofuro[2,3-b]furan-5-yl]-2,3-dimethyl-5-prop-1-en-2-ylcyclohexan-1-one
• CAS: 213833-81-9
• 化学式: C₁₇H₂₆O₃
• 分子量: 278.392
• InChiKey: SRJZJMHOJKRFMF-DCKPPDLLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  20
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (2R,3R,5R)-2-[(2R,3aS,6aR)-hexahydrofuro[2,3-b]furan-2-yl]-5-isopropenyl-2,3-dimethylcyclohexane 在 palladium on activated charcoal 盐酸羟胺 、 氢气 、 sodium acetate 、 sodium hydride 、 臭氧 作用下， 以 甲醇 、 乙醚 、 乙醇 、 二氯甲烷 、 氯仿 、 乙酸乙酯 为溶剂， 反应 33.0h， 生成 (6R,7R)-7-[(2R,3aS,6aR)-hexahydrofuro[2,3-b]furan-2-yl]-6,7-dimethyl-4,5,6,7-tetrahydrobenzo[d]isoxazole
  参考文献：
  名称：

  衍生自R -（-）-香芹酮的取代环己酮的Robinson环糊法合成官能化十萘醌的对映选择性

  摘要：

  铜催化将碘化甲基镁的共轭加成到环己烯酮中并捕获烯醇化物作为其三甲基甲硅烷基烯醇醚，然后由三苯甲基六氯锑酸酯（TrSbCl 6）催化的Mukaiyama反应用于R -（-）-香芹酮。事实证明，这是制备C-2，C-3官能化手性环己酮的有效方法。这些化合物被转化为其α-氰基酮，然后与甲基乙烯基酮进行罗宾逊环化反应。研究了这些环行的范围和局限性。获得了一系列高度官能化的手性十萘烷，它们可以用作对映体纯净克拉多酮的总合成中的起始化合物。

  DOI：

  10.1016/s0040-4020(00)00110-1
• 作为产物：
  描述：

  (+/-)-cis,trans-toluene-4-sulfonic acid (2-methoxytetrahydrofuran-3-yl)methyl ester 在 sodium hydroxide 、 trityl perchlorate 、 二异丁基氢化铝 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 101.58h， 生成 (2R,3R,5R)-2-[(2R,3aS,6aR)-hexahydrofuro[2,3-b]furan-2-yl]-5-isopropenyl-2,3-dimethylcyclohexane
  参考文献：
  名称：

  Total Synthesis of Dihydroclerodin from (R)-(−)-Carvone

  摘要：

  The first total synthesis of the natural enantiomer of the insect-antifeedant dihydroclerodin (1) and lupulin C (40) has been achieved starting from (R)-(-)-carvone (2). In the applied strategy, the hexahydrofuro[2,3-b]furan moiety was introduced in an early stage of the synthesis. The correct configuration at C-9, C-11, C-13, and C-16 was established by application of a remarkably diastereoselective Mukaiyama reaction. The desired configuration at C-10 was obtained by catalytic reduction of the intermediate enone 21. After annulation of the second ring, the structural features at C-4, C-5, and C-6 were introduced. The successful finishing of the synthesis included a Chugaev elimination to give the exocyclic double bond at C-4 that is present in lupulin C. Oxidation of this double bond with m-CPBA afforded dihydroclerodin.

  DOI：

  10.1021/jo991151r

文献信息

• Enantioselective synthesis of highly functionalised cyclohexanones starting from R-(−)-carvone
  作者：Tommi M. Meulemans、Gerrit A. Stork、Ben J.M. Jansen、Aede de Groot

  DOI：10.1016/s0040-4039(98)01367-7

  日期：1998.9

  Copper (I) catalysed conjugate addition of methylmagnesium iodide to R-(−)-carvone and trapping the enolate as its trimethylsilyl enol ether, followed by a trityl perchlorate (TrClO4) catalysed Mukaiyama-aldol reaction, is an efficient method for the preparation of highly functionalised cyclohexanones which can be used as starting compounds in the total syntheses of enantiomerically pure clerodanes

  铜（I）催化的碘化甲基镁共轭加成到R-（-）-香芹酮中，并捕获烯醇化物作为其三甲基甲硅烷基烯醇醚，然后高氯酸三苯酯（TrClO 4）催化Mukaiyama- aldol反应，是制备的一种有效方法高度官能化的环己酮的衍生物，可以用作对映体纯净的立达酮的全部合成中的起始化合物。
• Enantioselective Synthesis of Functionalised Decalones by Robinson Annulation of Substituted Cyclohexanones, Derived from R-(−)-Carvone
  作者：Ben J.M Jansen、Cindy C.J Hendrikx、Nikolai Masalov、Gerrit A Stork、Tommi M Meulemans、Fliur Z Macaev、Aede de Groot

  DOI：10.1016/s0040-4020(00)00110-1

  日期：2000.3

  catalysed conjugate addition of methyl magnesium iodide to cyclohexenones and trapping of the enolate as its trimethylsilyl enol ether, followed by a trityl hexachloroantimonate (TrSbCl6) catalysed Mukaiyama-reaction, was applied to R-(−)-carvone. This proved to be an efficient method for the preparation of C-2, C-3 functionalised chiral cyclohexanones. These compounds were converted into their α-cyano ketones

  铜催化将碘化甲基镁的共轭加成到环己烯酮中并捕获烯醇化物作为其三甲基甲硅烷基烯醇醚，然后由三苯甲基六氯锑酸酯（TrSbCl 6）催化的Mukaiyama反应用于R -（-）-香芹酮。事实证明，这是制备C-2，C-3官能化手性环己酮的有效方法。这些化合物被转化为其α-氰基酮，然后与甲基乙烯基酮进行罗宾逊环化反应。研究了这些环行的范围和局限性。获得了一系列高度官能化的手性十萘烷，它们可以用作对映体纯净克拉多酮的总合成中的起始化合物。
• Total Synthesis of Dihydroclerodin from (<i>R</i>)-(−)-Carvone
  作者：Tommi M. Meulemans、Gerrit A. Stork、Fliur Z. Macaev、Ben J. M. Jansen、Aede de Groot

  DOI：10.1021/jo991151r

  日期：1999.12.1

  The first total synthesis of the natural enantiomer of the insect-antifeedant dihydroclerodin (1) and lupulin C (40) has been achieved starting from (R)-(-)-carvone (2). In the applied strategy, the hexahydrofuro[2,3-b]furan moiety was introduced in an early stage of the synthesis. The correct configuration at C-9, C-11, C-13, and C-16 was established by application of a remarkably diastereoselective Mukaiyama reaction. The desired configuration at C-10 was obtained by catalytic reduction of the intermediate enone 21. After annulation of the second ring, the structural features at C-4, C-5, and C-6 were introduced. The successful finishing of the synthesis included a Chugaev elimination to give the exocyclic double bond at C-4 that is present in lupulin C. Oxidation of this double bond with m-CPBA afforded dihydroclerodin.