(1S,2R,6S)-2-羟基-4-(3-甲基丁-3-烯-1-炔基)-7-氧杂双环[4.1.0]庚-3-烯-5-酮 | 125555-67-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: (1S,2R,6S)-2-羟基-4-(3-甲基丁-3-烯-1-炔基)-7-氧杂双环[4.1.0]庚-3-烯-5-酮
• 英文名称: (-)-harveynone
• 英文别名: (1S,5R,6S)-5-hydroxy-3-(3-methylbut-3-en-1-ynyl)-7-oxabicyclo[4.1.0]hept-3-en-2-one
• CAS: 125555-67-1
• 化学式: C₁₁H₁₀O₃
• 分子量: 190.199
• InChiKey: PQAVKHOYIGJVBH-DVVUODLYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  49.8
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  (1R,2S,4S,6R,7R,8R,9S)-7-[tert-butyl(dimethyl)silyl]oxy-5-oxatetracyclo[7.2.1.02,8.04,6]dodec-10-en-3-one 在 吡啶 、 N-甲基吡咯烷酮 、 bis-triphenylphosphine-palladium(II) chloride 、 copper(l) iodide 、 氢氟酸 、 碘 作用下， 以 二苯醚 、 二氯甲烷 、 乙腈 为溶剂， 生成 (1S,2R,6S)-2-羟基-4-(3-甲基丁-3-烯-1-炔基)-7-氧杂双环[4.1.0]庚-3-烯-5-酮
  参考文献：
  名称：

  Absolute Configuration of (+)-PT-Toxin: Enantiodivergent Synthesis of (+)- and (-)-PT-Toxins

  摘要：

  DOI：

  10.3987/com-97-s(n)5

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 reactions of highly oxygenated vinyl halides: The first synthesis of harveynone and epi-harveynone
  作者：Andrew E. Graham、Darren McKerrecher、D.Huw Davies、Richard J.K. Taylor

  DOI：10.1016/0040-4039(96)01607-3

  日期：1996.10

  Sonogashira coupling reactions of highly functionalised cyclohexenyl halides have been developed and utilised to prepare the naturally-occurring anti-cancer agent harveynone and its C-4 epimer.

  已开发出高度官能化的环己烯基卤化物的Sonogashira偶联反应，并用于制备天然存在的抗癌药harveynone及其C-4差向异构体。
• Chemoenzymatic Access to Versatile Epoxyquinol Synthons
  作者：David M. Pinkerton、Martin G. Banwell、Anthony C. Willis

  DOI：10.1021/ol9016657

  日期：2009.10.1

  The enantiomerically pure and readily available metabolites 10-12 have been converted over four simple steps into the epoxyquinol derivatives 22-24, respectively. Compounds 23 and 24 or their immediate precursors have been exploited in efficient total syntheses of (-)-bromoxone (ent-1), (-)-epiepoformin (ent-2), (-)-harveynone (4), (+)-panepophenanthrin (6), and (+)-hexacyclinol (9).
• 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
• Tandem Enyne Metathesis−Metallotropic [1,3]-Shift for a Concise Total Syntheses of (+)-Asperpentyn, (−)-Harveynone, and (−)-Tricholomenyn A
  作者：Jingwei Li、Sangho Park、Reagan L. Miller、Daesung Lee

  DOI：10.1021/ol802675j

  日期：2009.2.5

  A tandem reaction sequence involving relay metathesis-induced enyne RCM and metallotropic [1,3]-shift is an effective tool to construct cyclic alkenes with embedded 1,5-dien-3-yne moieties from acyclic precursors containing a 1,3-diyne. Total syntheses of (+)-asperpentyn, (-)-harveynone, and (-)-tricholomenyn A have been accomplished by implementing this metathesis-based tandem reaction sequence as the key step.