(2R,3S,4S)-4-[(tert-Butyldimethylsilyl)oxy]-2,3-epoxy-6-(3-methylbut-3-en-1-ynyl)-5-cyclohexen-1-one | 188308-08-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (2R,3S,4S)-4-[(tert-Butyldimethylsilyl)oxy]-2,3-epoxy-6-(3-methylbut-3-en-1-ynyl)-5-cyclohexen-1-one
• 英文别名: (1R,5S,6S)-5-[tert-butyl(dimethyl)silyl]oxy-3-(3-methylbut-3-en-1-ynyl)-7-oxabicyclo[4.1.0]hept-3-en-2-one
• CAS: 188308-08-9
• 化学式: C₁₇H₂₄O₃Si
• 分子量: 304.461
• InChiKey: PHEPGDGVPLOBIG-IMJJTQAJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.23
• 重原子数：
  21
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.59
• 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：

  (2R,3S,4S)-4-[(tert-Butyldimethylsilyl)oxy]-2,3-epoxy-6-(3-methylbut-3-en-1-ynyl)-5-cyclohexen-1-one 在 氢氟酸 作用下， 以 乙腈 为溶剂， 反应 2.0h， 以92%的产率得到(2R,3S,4S)-2,3-Epoxy-4-hydroxy-6-(3-methylbut-3-en-1-ynyl)-5-cyclohexen-1-one
  参考文献：
  名称：

  生物活性环氧醌天然产物（+）-harveynone和（-）-asperpentyn的对映选择性合成

  摘要：

  报告了（+）-harveynone和（-）-asperpentyn的立体和对映选择性合成。

  DOI：

  10.1016/j.tetlet.2012.05.115
• 作为产物：
  描述：

  (3aR,7R,7aS)-7-hydroxy-2,2-dimethyltetrahydrobenzo[d][1,3]dioxol-5(6H)-one 在 bis-triphenylphosphine-palladium(II) chloride 吡啶 、 咪唑 、 4-二甲氨基吡啶 、 sodium hydroxide 、 copper(l) iodide 、 碘 作用下， 以 四氢呋喃 、 四氯化碳 、 N,N-二甲基甲酰胺 为溶剂， 反应 28.0h， 生成 (2R,3S,4S)-4-[(tert-Butyldimethylsilyl)oxy]-2,3-epoxy-6-(3-methylbut-3-en-1-ynyl)-5-cyclohexen-1-one
  参考文献：
  名称：

  The First Synthesis of (−)-Asperpentyn and Efficient Syntheses of (+)-Harveynone, (+)-Epiepoformin and (−)-Theobroxide

  摘要：

  A generally applicable strategy for the synthesis of a range of polyoxygenated cyclohexane natural products has been developed. The enantioselective syntheses of (-)-theobroxide, a polyoxygenated cyclohexane natural compound with potent growth inducing properties in potato microtubers has been achieved via a 1,2 O-silyl migration between trans-hydroxyl groups and a remote hydroxyl directed epoxidation of an enone derived from quinic acid. A thus derived alpha -iodoenone was subjected to Stille coupling with tetramethylstannane to afford the first title compound. A similar strategy enabled a route to the complete asymmetric synthesis of the acetylenic phytotoxin (+)-harveynone. By selective reduction of (-)-theobroxide, (+)-epiepoformin was also prepared in enantiopure form and similarly, stereoselective reduction of (+)-harveynone completed the first enantioselective synthesis of (-)-asperpentyn, another natural compound with antimicrobial activity.

  DOI：

  10.1002/1521-3765(20001103)6:21<3991::aid-chem3991>3.3.co;2-m

文献信息

• Strictly Regiocontrolled α-Monosubstitution of Cyclic Carbonyl Compounds with Alkynyl and Alkyl Groups via Pd-Catalyzed Coupling of Cyclic α-Iodoenones with Organozincs
  作者：Ei-ichi Negishi、Ze Tan、Show-Yee Liou、Baiqiao Liao

  DOI：10.1016/s0040-4020(00)00864-4

  日期：2000.12

  derivatives readily undergo Pd-catalyzed cross coupling with α-iodoenones. Although (s-Bu)2Zn also undergoes Pd-catalyzed cross coupling, only the n-Bu-substituted products were obtained. α-Benzylation and α-homobenzylation can proceed satisfactorily, whereas allylzinc and propargylzinc derivatives undergo only addition to the carbonyl group. Although some promising results have been obtained in α-homoallylation

  已优化了Pd催化的环状α-碘烯酮（如2-碘-2-环己烯酮）与炔基锌的交叉偶联条件。使用三（邻-呋喃基）膦（TFP）作为配体和使用DMF作为溶剂已导致以优异的产率形成α-炔基酮。该最优化的方法已用于高产率合成（±）-harveynone和（±）-tricholomenynA。对使用烷基锌的相关α-烷基化反应的研究揭示了以下内容。甲基锌和伯烷基锌衍生物容易与α-碘烯酮进行Pd催化的交叉偶联。尽管（s -Bu）2 Zn也经历Pd催化的交叉偶联，但只有n获得-Bu-取代的产物。α-苄基化和α-高苄基化可以令人满意地进行，而烯丙基锌和炔丙基锌衍生物仅在羰基上加成。尽管已经在α-均烯丙基化和α-均丙炔化中获得了一些有希望的结果，但是这些反应仍需要进一步改善。
• Sonogashira Coupling of 2-Iodo-2-cycloalkenones:  Synthesis of (+)- and (−)-Harveynone and (−)-Tricholomenyn A
  作者：Michael W. Miller、Carl R. Johnson

  DOI：10.1021/jo962295y

  日期：1997.3.1
• Absolute Configuration of (+)-PT-Toxin: Enantiodivergent Synthesis of (+)- and (-)-PT-Toxins
  作者：Kunio Ogasawara、Takashi Kamikubo

  DOI：10.3987/com-97-s(n)5

  日期：——
• Enantioselective syntheses of bioactive epoxyquinone natural products (+)-harveynone and (−)-asperpentyn
  作者：Goverdhan Mehta、Subhrangsu Roy、Subhas Chandra Pan

  DOI：10.1016/j.tetlet.2012.05.115

  日期：2012.8

  Stereo- and enantioselective syntheses of (+)-harveynone and (−)-asperpentyn are reported.

  报告了（+）-harveynone和（-）-asperpentyn的立体和对映选择性合成。
• The First Synthesis of (−)-Asperpentyn and Efficient Syntheses of (+)-Harveynone, (+)-Epiepoformin and (−)-Theobroxide
  作者：M. Teresa Barros、Christopher D. Maycock、M. Rita Ventura

  DOI：10.1002/1521-3765(20001103)6:21<3991::aid-chem3991>3.3.co;2-m

  日期：2000.11.3

  A generally applicable strategy for the synthesis of a range of polyoxygenated cyclohexane natural products has been developed. The enantioselective syntheses of (-)-theobroxide, a polyoxygenated cyclohexane natural compound with potent growth inducing properties in potato microtubers has been achieved via a 1,2 O-silyl migration between trans-hydroxyl groups and a remote hydroxyl directed epoxidation of an enone derived from quinic acid. A thus derived alpha -iodoenone was subjected to Stille coupling with tetramethylstannane to afford the first title compound. A similar strategy enabled a route to the complete asymmetric synthesis of the acetylenic phytotoxin (+)-harveynone. By selective reduction of (-)-theobroxide, (+)-epiepoformin was also prepared in enantiopure form and similarly, stereoselective reduction of (+)-harveynone completed the first enantioselective synthesis of (-)-asperpentyn, another natural compound with antimicrobial activity.