trans-5-hydroxy-5-phenylpent-3-en-2-one | 57204-68-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: trans-5-hydroxy-5-phenylpent-3-en-2-one
• 英文别名: (E)-5-hydroxy-5-phenylpent-3-en-2-one
• CAS: 57204-68-9
• 化学式: C₁₁H₁₂O₂
• 分子量: 176.215
• InChiKey: SFAMZEMIAZHKEY-BQYQJAHWSA-N

物化性质

• 沸点：
  341.6±42.0 °C(Predicted)
• 密度：
  1.096±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.18
• 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：

  聚合甲醛 、 trans-5-hydroxy-5-phenylpent-3-en-2-one 在 bismuth (III) nitrate pentahydrate 作用下， 以 二氯甲烷 为溶剂， 反应 36.0h， 以60%的产率得到1-(5-phenyl-1,3-dioxolan-4-yl)propan-2-one
  参考文献：
  名称：

  Diastereoselective construction of anti-4,5-disubstituted-1,3-dioxolanes via a bismuth-mediated two-component hemiacetal oxa-conjugate addition of γ-hydroxy-α,β-unsaturated ketones with paraformaldehyde

  摘要：

  铋介导的两组分半缩醛氧共轭加成为选择性构建反式-4,5-二取代1,3-二氧杂环戊烷提供了一种温和的方法。

  DOI：

  10.1039/c5cc01949d
• 作为产物：
  描述：

  1-苯基-2-丙烯-1-醇 、 丁烯酮 在 Hoveyda-Grubbs catalyst second generation 作用下， 以 二氯甲烷 为溶剂， 反应 4.0h， 生成 trans-5-hydroxy-5-phenylpent-3-en-2-one
  参考文献：
  名称：

  Diastereoselective construction of anti-4,5-disubstituted-1,3-dioxolanes via a bismuth-mediated two-component hemiacetal oxa-conjugate addition of γ-hydroxy-α,β-unsaturated ketones with paraformaldehyde

  摘要：

  铋介导的两组分半缩醛氧共轭加成为选择性构建反式-4,5-二取代1,3-二氧杂环戊烷提供了一种温和的方法。

  DOI：

  10.1039/c5cc01949d

文献信息

• An expedient route to substituted furans via olefin cross-metathesis
  作者：Timothy J. Donohoe、John F. Bower

  DOI：10.1073/pnas.0913466107

  日期：2010.2.23

  of highly substituted derivatives are essential to medicinal chemistry. Here we show that the olefin CM reaction, in combination with an acid cocatalyst or subsequent Heck arylation, provides a concise and flexible entry to 2,5-di- or 2,3,5-tri-substituted furans. These cascade processes portend further opportunities for the regiocontrolled preparation of other highly substituted aromatic and heteroaromatic

  烯烃交叉复分解 (CM) 反应广泛用于有机化学，是选择性合成差异取代烯烃产物的有效方法。令人惊讶的是，尚未报道将这一非凡的过程整合到芳香族和杂芳香族构建策略中的努力。这种结构代表了大多数小分子药物化合物的关键要素；高度取代衍生物的受控制备方法对于药物化学是必不可少的。在这里，我们展示了烯烃 CM 反应与酸助催化剂或随后的 Heck 芳基化相结合，为 2,5-二-或 2,3,5-三-取代呋喃提供了简洁而灵活的入口。
• Chromium-mediated coupling and application to the synthesis of halichondrins
  申请人：President and Fellows of Harvard College

  公开号：US10344038B2

  公开（公告）日：2019-07-09

  The present invention provides unified synthesis of the CI-CI 9 building blocks of halichondrins and analogs thereof using selective coupling of poly-halogenated nucleophiles in chromium-mediated coupling reactions. The present invention also provides a practical and efficient synthesis of C20-C38 building blocks of halichondrins and analogs thereof. Also provided herein are general methods of selective activation and coupling of poly-halogenated analogs with an aldehyde. The provided coupling reactions are selective for halo-enone and halo-acetylenic ketal over vinyl halide and halide attached to a sp hydridized carbon. The provided efficient selective coupling reactions can allow easy access to the CI-CI 9 building blocks and C20-C38 building blocks of halichondrins and analogs thereof with limited or no purification or separation of the intermediates.

  本发明提供了在铬介导的偶联反应中利用多卤代亲核物的选择性偶联来统一合成卤代姜黄素及其类似物的 CI-CI 9 结构单元。本发明还提供了一种实用高效的卤代龙毒素及其类似物的 C20-C38 结构单元的合成方法。本发明还提供了选择性活化多卤代类似物并将其与醛偶联的一般方法。所提供的偶联反应对卤代烯酮和卤代乙炔缩酮具有选择性，而对乙烯基卤化物和连接到 sp 水化物碳上的卤化物则没有选择性。所提供的高效选择性偶联反应可以方便地获得卤代烯酮及其类似物的 CI-CI 9 结构单元和 C20-C38 结构单元，中间产物的纯化或分离程度有限或根本不需要。
• Cu^I/Rh^II-Catalyzed Tandem Convergent Multicomponent Reaction for the Regio- and Stereocontrolled Synthesis of γ-Oxo-β-amino Esters
  作者：Da Jung Jung、Hyun Ji Jeon、Joo Hyun Lee、Sang-gi Lee

  DOI：10.1021/acs.orglett.5b01587

  日期：2015.7.17

  The first example of a highly regio- and stereo-selective catalytic method for the three-component one-pot synthesis of highly functionalized alpha-vinylated gamma-oxo-beta-amino esters is disclosed. In this catalytic triad, the Cu-I-catalyst selectively catalyzes the, cycloaddition of the 1-alkyne and sulfonyl azide first resulting in the corresponding 1-sulfonyl-1,2,3-triazole. An a-imino Rh-II-carbene is generated from an open-chain alpha-imino diazo of the triazole, and this species reacts with gamma-hydroxy alpha,beta-unsaturated esters to form allylic (Z)-amino vinyl ethers. Rapid deconjugative [3,3]-sigmatropic rearrangement affords the alpha-vinyl gamma-oxo-beta-amino esters in high yields with high levels of diastereoselectivity.
• CHROMIUM-MEDIATED COUPLING AND APPLICATION TO THE SYNTHESIS OF HALICHONDRINS
  申请人：President and Fellows of Harvard College

  公开号：US20200031843A1

  公开（公告）日：2020-01-30

  The present invention provides unified synthesis of the C1-C19 building blocks of halichondrins and analogs thereof using selective coupling of poly-halogenated nucleophiles in chromium-mediated coupling reactions. The present invention also provides a practical and efficient synthesis of C20-C38 building blocks of halichondrins and analogs thereof. Also provided herein are general methods of selective activation and coupling of poly-halogenated analogs with an aldehyde. The provided coupling reactions are selective for halo-enone and halo-acetylenic ketal over vinyl halide and halide attached to a sp hybridized carbon. The provided efficient selective coupling reactions can allow easy access to the C1-C19 building blocks and C20-C38 building blocks of halichondrins and analogs thereof with limited or no purification or separation of the intermediates.