3-(dimethyl-phenyl-silyl)-pent-4-enoic acid methyl ester | 222300-38-1

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: 3-(dimethyl-phenyl-silyl)-pent-4-enoic acid methyl ester
• 英文别名: 3-(dimethylphenylsilyl)pent-4-enoic acid methyl ester；methyl 3-(dimethyl(phenyl)silyl)pent-4-enoate；Methyl 3-[dimethyl(phenyl)silyl]pent-4-enoate
• CAS: 222300-38-1
• 化学式: C₁₄H₂₀O₂Si
• 分子量: 248.397
• InChiKey: CFVXSOZYKRFSRV-UHFFFAOYSA-N

物化性质

• 沸点：
  308.6±35.0 °C(Predicted)
• 密度：
  0.96±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.72
• 重原子数：
  17
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3-(dimethyl-phenyl-silyl)-pent-4-enoic acid methyl ester 在 四(三苯基膦)钯 lithium aluminium tetrahydride 、 正丁基锂 、 p-tolyl benzeneselenosulfonate 、 二异丙胺 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 正己烷 、 二氯甲烷 为溶剂， 反应 5.5h， 生成 [2-(dimethyl(phenyl)silyl)-3-(tosylmethyl)-4-vinylcyclopentyl]methanol
  参考文献：
  名称：

  Free-Radical-5-exo-Trig Cyclization of Chiral 3-Silylhepta-1,6-dienes:  Concise Approach to the A−B−C Ring Core of Hexacyclinic Acid

  摘要：

  Free-radical-mediated 5-exo-trig cyclization of hepta-1,6-dienes 6a-c incorporating an allylsilane moiety was shown to provide at low temperature exclusively the trans-cis cyclopentanes 7a-c in good yield. In contrast, the same reaction with the alkyl analogue 9a led to the formation of all four possible stereoisomers. Interestingly, extension of this sequence of radical processes to alkoxy analogues 12-14 provided the complementary cis-cis stereoisomers with modest to excellent stereoselectivity. It is noteworthy that under such conditions allylsilanes were found to be much more reactive than their alkyl and alkoxy analogues. Beckwith-Houk-type models were proposed that rationalize the stereochemical course of these 5-exo-trig cyclizations. Finally, an illustration of the value of this methodology was proposed with the synthesis of the A-B-C tricyclic unit of polyketide hexacyclinic acid 3a.

  DOI：

  10.1021/jo051062g
• 作为产物：
  描述：

  原乙酸三甲酯 、 3-[二甲基(苯基)甲硅烷基]丙-2-烯-1-醇 在 丙酸 作用下， 以 甲苯 为溶剂， 以67%的产率得到3-(dimethyl-phenyl-silyl)-pent-4-enoic acid methyl ester
  参考文献：
  名称：

  硅基对自由基5-exo-trig环化的立体选择性的显着影响。

  摘要：

  [反应：见正文]已显示手性3-甲硅烷基庚-1,6-二烯的磺酰基自由基介导的5-exo-trig环化可提供具有多达四个立体生成中心的环戊烷，其立体控制水平出乎意料地高。

  DOI：

  10.1021/ol036025v

文献信息

• Synthesis of Fused Piperidinones through a Radical-Ionic Cascade
  作者：Edouard Godineau、Kurt Schenk、Yannick Landais

  DOI：10.1021/jo801308j

  日期：2008.9.19

  were observed, demonstrating the ability of a silicon group located at the allylic position to efficiently control the stereochemistry of the two newly created stereogenic centers. When the radical cascade was extended to ketoximes, the resulting sterically hindered alkoxyaminyl radical did not react further with the initiator Et3B to produce the expected nucleophilic amidoborane complex. In sharp contrast

  使用立体控制的形式[2 + 2 + 2]自由基离子过程，从具有肟部分的手性烯丙基硅烷中组装出氮杂双环[4.3.0]壬烷。级联反应包括向烯肟的较少取代的末端添加α-碘酸酯，然后在醛肟官能团上进行5-exo-trig环化，产生烷氧基氨基烷基团，最后内酰胺化，得到标题的哌啶酮。观察到高水平的立体诱导，表明位于烯丙基位置的硅基团有效控制两个新创建的立体发生中心的立体化学的能力。当自由基级联扩展至酮肟时，所得的空间位阻的烷氧基氨基基团不会进一步与引发剂Et3B反应生成预期的亲核性氨基硼烷络合物。与之形成鲜明对比的是，该长寿命基团与初始的α-稳定的酯基团重新结合，生成了一个包含两个酯片段的环戊烷。
• Radical-Mediated 5-<i>E</i><i>xo</i>-<i>Trig</i> Cyclizations of 3-Silylhepta-1,6-dienes
  作者：Philippe James、Kurt Schenk、Yannick Landais

  DOI：10.1021/jo060024+

  日期：2006.4.1

  radical mediated 5-exo-trig cyclization of 3-silylheptadienyl systems 3a−d has been studied. At low temperature, the reaction of the sulfonyl radical occurs regioselectively at the allylsilane terminus, while a reversal of regioselectivity is observed at 80 °C. This general trend has been rationalized on the basis of polar effects and radical stabilization. Thiyl-mediated radical cyclization of dienes 3a

  研究了磺酰基自由基介导的3-甲硅烷基庚二烯基体系3a - d的5- exo - trig环化的区域选择性。在低温下，磺酰基的反应在烯丙基硅烷末端发生区域选择性，而在80°C时则观察到区域选择性的逆转。在极性影响和自由基稳定的基础上，已对这一总体趋势进行了合理化。还研究了二硫醚3a，3c - d，7的巯基介导的自由基环化以及随后的硫原子转移，一步即可为噻双环[3.3.0]骨架提供出色的立体控制。
• Remarkable Effect of a Silicon Group on the Stereoselectivity of Radical <i>5-exo-</i>Trig Cyclizations
  作者：Philippe James、Yannick Landais

  DOI：10.1021/ol036025v

  日期：2004.2.1

  [reaction: see text] Sulfonyl radical mediated 5-exo-trig cyclization of chiral 3-silylhepta-1,6-dienes has been shown to provide cyclopentanes having up to four stereogenic centers with an unexpectedly high level of stereocontrol.

  [反应：见正文]已显示手性3-甲硅烷基庚-1,6-二烯的磺酰基自由基介导的5-exo-trig环化可提供具有多达四个立体生成中心的环戊烷，其立体控制水平出乎意料地高。
• Free-Radical-5-<i>exo</i>-Trig Cyclization of Chiral 3-Silylhepta-1,6-dienes:  Concise Approach to the A−B−C Ring Core of Hexacyclinic Acid
  作者：Philippe James、François-Xavier Felpin、Yannick Landais、Kurt Schenk

  DOI：10.1021/jo051062g

  日期：2005.9.1

  Free-radical-mediated 5-exo-trig cyclization of hepta-1,6-dienes 6a-c incorporating an allylsilane moiety was shown to provide at low temperature exclusively the trans-cis cyclopentanes 7a-c in good yield. In contrast, the same reaction with the alkyl analogue 9a led to the formation of all four possible stereoisomers. Interestingly, extension of this sequence of radical processes to alkoxy analogues 12-14 provided the complementary cis-cis stereoisomers with modest to excellent stereoselectivity. It is noteworthy that under such conditions allylsilanes were found to be much more reactive than their alkyl and alkoxy analogues. Beckwith-Houk-type models were proposed that rationalize the stereochemical course of these 5-exo-trig cyclizations. Finally, an illustration of the value of this methodology was proposed with the synthesis of the A-B-C tricyclic unit of polyketide hexacyclinic acid 3a.