trans-1-(phenylsulfonyl)-6-<(tert-butyldimethylsilyl)oxy>-1-hexene | 87640-86-6

• 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-1-(phenylsulfonyl)-6-<(tert-butyldimethylsilyl)oxy>-1-hexene
• 英文别名: (E)-6-[1-(tert-butyl)-1,1-dimethylosilyl]oxy-1-hexenyl phenyl sulfone；tert-butyl(dimethyl){[(E)-6-(phenylsulfonyl)-5-hexenyl]oxy}silane；trans-1-(phenylsulfonyl)-6-[(tert-butyldimethylsilyl)oxy]-1-hexene；[(E)-6-(benzenesulfonyl)hex-5-enoxy]-tert-butyl-dimethylsilane
• CAS: 87640-86-6
• 化学式: C₁₈H₃₀O₃SSi
• 分子量: 354.586
• InChiKey: HNMQSSVLSFYWCI-FOWTUZBSSA-N

物化性质

• 沸点：
  449.6±45.0 °C(Predicted)
• 密度：
  1.017±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.17
• 重原子数：
  23
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  51.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  trans-1-(phenylsulfonyl)-6-<(tert-butyldimethylsilyl)oxy>-1-hexene 在 disodium hydrogenphosphate 、 sodium amalgam 、 4-甲基苯磺酸吡啶 、 sodium hydride 、 对甲苯磺酸 作用下， 反应 89.0h， 生成 5-(4-hydroxybutyl)-4-<3-(trimethylsilyl)-2-butenyl>-3-cyclohexenone
  参考文献：
  名称：

  Regiocontrolled synthesis of mono-, di-, and trisubstituted cyclohexenones by cycloaddition of vinyl sulfones to 1-methoxy-3-[(trimethylsilyl)oxy]-1,3-butadienes. Conversion of alkenes into effective dienophilic reagents

  摘要：

  DOI：

  10.1021/jo00173a040
• 作为产物：
  描述：

  叔丁基(5-己烯基氧基)二甲基硅烷 以89%的产率得到trans-1-(phenylsulfonyl)-6-<(tert-butyldimethylsilyl)oxy>-1-hexene
  参考文献：
  名称：

  A vinyl sulfone-mediated diels-alder approach to the fully regiocontrolled elaboration of 4,5-disubstituted 2- and 3-cyclohexenones

  摘要：

  DOI：

  10.1016/s0040-4039(00)85776-7

文献信息

• Cross-metathesis reaction of vinyl sulfones and sulfoxides
  作者：Anna Michrowska、Michał Bieniek、Mikhail Kim、Rafał Klajn、Karol Grela

  DOI：10.1016/s0040-4020(03)00682-3

  日期：2003.6

  Cross-metathesis reactions of α,β-unsaturated sulfones and sulfoxides in the presence of molybdenum and ruthenium pre-catalysts were tested. A selective metahesis reaction was achieved between functionalized terminal olefins and vinyl sulfones by using the ‘second generation’ ruthenium catalysts 1c–h while the highly active Schrock catalyst 1b was found to be functional group incompatible with vinyl

  测试了在钼和钌预催化剂存在下α，β-不饱和砜和亚砜的交叉复分解反应。通过使用“第二代”钌催化剂1c - h，在官能化的末端烯烃和乙烯基砜之间实现了选择性的复分解反应，而高活性的Schrock催化剂1b是与乙烯基砜不相容的官能团。交叉复分解产物以良好的产率分离并具有优异的（E）选择性。但是，钼和钌基络合物均与α，β-和β，γ-不饱和亚砜不相容。
• A Good Bargain: An Inexpensive, Air-Stable Ruthenium Metathesis Catalyst Derived from α-Asarone
  作者：Karol Grela、Mikhail Kim

  DOI：10.1002/ejoc.200390151

  日期：2003.3

  The one-step synthesis of ruthenium carbene precatalyst 7 from inexpensive α-asarone [(E)-6] is described. This recyclable and easy to obtain complex can be used successfully in various types of metathesis (RCM, CM, enyne) as a cheaper and more potent substitute of the Hoveyda-type precatalyst 2b. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

  描述了从廉价的 α-细辛酮 [(E)-6] 一步合成钌卡宾预催化剂 7。这种可回收且易于获得的复合物可成功用于各种类型的复分解（RCM、CM、烯炔），作为 Hoveyda 型预催化剂 2b 的更便宜且更有效的替代品。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
• In an Attempt to Provide a User's Guide to the Galaxy of Benzylidene, Alkoxybenzylidene, and Indenylidene Ruthenium Olefin Metathesis Catalysts
  作者：Michał Bieniek、Anna Michrowska、Dmitry L. Usanov、Karol Grela

  DOI：10.1002/chem.200701340

  日期：2008.1.18

  tested. Interestingly, attempts to force a reaction by increasing the catalyst loading were much less effective. Therefore, when possible, it is suggested that metathesis transformations should be carried out with a second-generation catalyst at 70 degrees C in toluene. However, different second-generation catalysts proved to be optimal for different applications and no single catalyst outperformed all others

  本文报道的数据表明，为给定的复分解反应选择合适的催化剂时必须格外小心。发现第一代催化剂可用于空间不受阻碍的底物的复分解反应。第二代催化剂（在优化条件下）对于不使用第一代配合物反应的空间位阻和吸电子基团（EWG）取代的烯烃表现出良好至优异的活性。在所有测试的反应中均观察到强烈的温度效应。有趣的是，试图通过增加催化剂负载来强迫反应的效果要差得多。因此，在可能的情况下，建议应使用第二代催化剂在70摄氏度的甲苯中进行复分解转化。然而，事实证明，不同的第二代催化剂对于不同的应用是最佳的，并且在所有情况下，没有任何一种催化剂能胜过所有其他催化剂。然而，可以从模型实验中得出一些经验规则，为选择最佳催化剂提供了初步提示。
• Nitro-Substituted Hoveyda−Grubbs Ruthenium Carbenes:  Enhancement of Catalyst Activity through Electronic Activation
  作者：Anna Michrowska、Robert Bujok、Syuzanna Harutyunyan、Volodymyr Sashuk、Grigory Dolgonos、Karol Grela

  DOI：10.1021/ja048794v

  日期：2004.8.1

  The design, synthesis, stability, and catalytic activity of nitro-substituted Hoveyda-Grubbs metathesis catalysts are described. The highly active and stable meta- and para-substituted complexes are attractive from a practical point of view. These catalysts operate in very mild conditions and can be successfully applied in various types of metathesis [ring-closing metathesis, cross-metathesis (CM), and enyne metathesis]. Although the presence of a NO2 group leads to catalysts that are dramatically more active than both the second-generation Grubbs's catalyst and the phosphine-free Hoveyda's carbene, enhancement of reactivity is somewhat lower than that observed for a sterically activated Hoveyda-Grubbs catalyst. Attempts to combine two modes of activation, steric and electronic, result in severely decreasing a catalyst's stability. The present findings illustrate that different Ru catalysts turned out to be optimal for different applications. Whereas phosphine-free carbenes are catalysts of choice for CM of various electron-deficient substrates, they exhibit lower reactivity in the formation of tetrasubstituted double bonds. This demonstrates that no single catalyst outperforms all others in all possible applications.
• Highly selective cross-metathesis with phenyl vinyl sulphone using the ‘second generation’ Grubbs’ catalyst
  作者：Karol Grela、Michał Bieniek

  DOI：10.1016/s0040-4039(01)01269-2

  日期：2001.9

  A cross-metathesis reaction was achieved between functionalised terminal olefins and phenyl vinyl sulfone by using the commercially available ruthenium catalyst Ile. The cross-metathesis products were isolated in moderate to good yield with excellent (E)-stereoselectivity. (C) 2001 Elsevier Science Ltd. All rights reserved.