tert-butyl(hex-4-yn-1-yloxy)dimethylsilane | 132645-60-4

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: tert-butyl(hex-4-yn-1-yloxy)dimethylsilane
• 英文别名: Tert-butyl-hex-4-ynoxy-dimethylsilane
• CAS: 132645-60-4
• 化学式: C₁₂H₂₄OSi
• 分子量: 212.407
• InChiKey: QSNBGCAGDXTNBG-UHFFFAOYSA-N

物化性质

• 沸点：
  232.6±23.0 °C(Predicted)
• 密度：
  0.842±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.81
• 重原子数：
  14
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  tert-butyl(hex-4-yn-1-yloxy)dimethylsilane 在 sodium hypochlorite 、 sodium chlorite 、 2,2,6,6-四甲基哌啶氧化物 、 氢氟酸 作用下， 以 水 、 乙腈 为溶剂， 反应 5.5h， 生成 4-己炔酸
  参考文献：
  名称：

  Stereoselective Synthesis of 5-(1-Hydroxyalkyl)-2-pyrrolidinones Utilizing Oxidation of 5-Alkylidene-2-pyrrolidinones to Acyliminium Ion Precursors

  摘要：

  A general method was devised for the LiN(TMS)(2)/AgOTf (=2:1)-catalyzed intramolecular (5-exo-dig) cyclization of beta -alkynylamides 1 possessing alkyl, aryl or no functional groups at the terminal alkynes, to 5-alkylidene-2-pyrrolidinones 2. These 5-alkylidene-2-pyrrolidinones were oxidized to the diol-type alkoxylactams 3 by dimethyldioxirane (DMD) or mCPBA in MeOH. These alkoxylactams are useful as tertiary N-acyliminium ion precursors for the synthesis of threo-5-(1-hydroxyalkyl)-2-pyrrolidinone derivatives 5. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(00)00841-3
• 作为产物：
  描述：

  1-(tert-butyldimethylsilyloxy)-4-pentyne 、 碘甲烷 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 、 六甲基磷酰三胺 为溶剂， 反应 11.5h， 以90%的产率得到tert-butyl(hex-4-yn-1-yloxy)dimethylsilane
  参考文献：
  名称：

  Stereoselective Synthesis of 5-(1-Hydroxyalkyl)-2-pyrrolidinones Utilizing Oxidation of 5-Alkylidene-2-pyrrolidinones to Acyliminium Ion Precursors

  摘要：

  A general method was devised for the LiN(TMS)(2)/AgOTf (=2:1)-catalyzed intramolecular (5-exo-dig) cyclization of beta -alkynylamides 1 possessing alkyl, aryl or no functional groups at the terminal alkynes, to 5-alkylidene-2-pyrrolidinones 2. These 5-alkylidene-2-pyrrolidinones were oxidized to the diol-type alkoxylactams 3 by dimethyldioxirane (DMD) or mCPBA in MeOH. These alkoxylactams are useful as tertiary N-acyliminium ion precursors for the synthesis of threo-5-(1-hydroxyalkyl)-2-pyrrolidinone derivatives 5. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(00)00841-3

文献信息

• Directed Regioselective Carbometallation of 1,2‐Dialkyl‐Substituted Cyclopropenes
  作者：Yair Cohen、Ilan Marek

  DOI：10.1002/anie.202111382

  日期：2021.12.6

  The copper-catalyzed carbomagnesiation reaction of cyclopropenes is a well-established method for the synthesis of stereodefined cyclopropanes. All existing reports to date proceeded towards the formation of the electronically more stable organometallic intermediate. Herein we report a regioselective addition to 1,2-dialkyl-substituted cyclopropene possessing a tethered directing group to direct the

  环丙烯的铜催化碳镁化反应是合成立体定义的环丙烷的成熟方法。迄今为止，所有现有报告都致力于形成电子更稳定的有机金属中间体。在此，我们报告了对 1,2-二烷基取代的环丙烯的区域选择性加成，该环丙烯具有系链导向基团，可将有机金属物种引导至两种电子无偏可能性中形成单一区域异构体中间体。
• Facile Preparation of Various Heteroaromatic Compounds via Azatitanacyclopentadiene Intermediates
  作者：Daisuke Suzuki、Youhei Nobe、Yuko Watai、Ryoichi Tanaka、Yuuki Takayama、Fumie Sato、Hirokazu Urabe

  DOI：10.1021/ja0502730

  日期：2005.5.25

  in a highly regioselective manner. Their subsequent reaction with sulfonylacetylene afforded pyridyltitanium compounds, which, upon reaction with electrophiles, gave substituted pyridines virtually as a single isomer. When optically active nitriles were used in this reaction, chiral pyridines were obtained without loss of the enantiopurity. Alternatively, the azatitanacyclopentadiene prepared from an

  乙炔、腈和钛试剂 Ti(Oi-Pr)(4)/2 i-PrMgCl 的偶联以高度区域选择性的方式生成了新的氮杂钛烷环戊二烯。它们随后与磺酰乙炔反应得到吡啶基钛化合物，在与亲电子试剂反应时，得到取代的吡啶，实际上是单一异构体。当在该反应中使用旋光腈时，可以在不损失对映体纯度的情况下获得手性吡啶。或者，由不对称乙炔制备的氮杂钛烷环戊二烯与醛或另一种腈反应，再次以区域选择性方式得到具有四个不同取代基的呋喃或吡咯。
• Nickel(0)-catalyzed synthesis of substituted phenols from cyclobutenones and alkynes
  作者：Mark A. Huffman、Lanny S. Liebeskind

  DOI：10.1021/ja00007a072

  日期：1991.3

  The results above show that the convergent synthesis of substituted phenols is possible by nickel(0)-catalyzed ring opening and cycloaddition of cyclobutenones with alkynes. Future efforts will explore application of this method to intramolecular reactions

  上述结果表明，通过镍（0）催化的环丁烯酮与炔烃的开环和环加成反应，可以聚合合成取代酚。未来的努力将探索这种方法在分子内反应中的应用
• Rhodium/Lewis Acid Catalyzed Regioselective Addition of 1,3-Dicarbonyl Compounds to Internal Alkynes
  作者：Wei-Feng Zheng、Qiu-Jing Xu、Qiang Kang

  DOI：10.1021/acs.organomet.7b00284

  日期：2017.6.26

  regioselective addition of 1,3-dicarbonyl compounds to internal alkynes catalyzed by rhodium/Lewis acid catalysts. The corresponding branched/linear allylic alkylation products could be selectively obtained in good yields. Rh–H species were considered to be generated by direct C–H oxidative addition of 1,3-dicarbonyl compounds with rhodium catalyst with the assistance of Lewis acid. Moreover, a retro-allylic

  在本文中，我们描述了将铑/路易斯酸催化剂将1，3-二羰基化合物区域选择性加成至内部炔烃的有效方案。可以高收率选择性地获得相应的支链/线性烯丙基烷基化产物。Rh-H物质被认为是通过在路易斯酸的辅助下用铑催化剂直接1，H-二羰基化合物的CH-H氧化加成反应而产生的。此外，在该转化中观察到了逆烯丙基烷基化过程。
• Tandem Rh-catalysis: decarboxylative β-keto acid and alkyne cross-coupling
  作者：Faben A. Cruz、Zhiwei Chen、Sarah I. Kurtoic、Vy M. Dong

  DOI：10.1039/c6cc02522f

  日期：——

  Herein, we describe a regioselective Rh-catalyzed decarboxylative cross-coupling of [small beta]-keto acids and alkynes to access branched [gamma],[small delta]-unsaturated ketones. Rh-hydride catalysis enables the isomerization of an alkyne to generate a metal-allyl...

  在本文中，我们描述了小β-酮酸和炔的区域选择性Rh催化的脱羧交叉偶联以进入支链的γ，β-不饱和酮。氢化铑催化能够使炔烃异构化以生成金属烯丙基...