ethyl 3-(triisopropylsilyl)propiolate | 500297-71-2

• 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: ethyl 3-(triisopropylsilyl)propiolate
• 英文别名: ethyl 3-tri(propan-2-yl)silylprop-2-ynoate
• CAS: 500297-71-2
• 化学式: C₁₄H₂₆O₂Si
• 分子量: 254.445
• InChiKey: PJEZBPMKVNUQEO-UHFFFAOYSA-N

物化性质

• 沸点：
  286.6±9.0 °C(Predicted)
• 密度：
  0.898±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.77
• 重原子数：
  17.0
• 可旋转键数：
  4.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.79
• 拓扑面积：
  26.3
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  ethyl 3-(triisopropylsilyl)propiolate 在 二异丁基氢化铝 作用下， 以 二氯甲烷 为溶剂， 以85%的产率得到3-(三异丙硅基)丙炔醛
  参考文献：
  名称：

  Total Regio- and Diastereocontrol in the Aldol Reactions of Dienolborinates

  摘要：

  It is reported that appropriate dienolborinates can provide access to both diastereomers of 2-(hydroxymethyl)but-3-enoates through exclusive alpha-regiocontrol in a non-vinylogous pathway. Contrary to previous reports in which dialkylchloroboranes failed to enolize propanoates, acidity-enhanced but-3-enoates readily undergo enolization, offering unprecedented control over the formation of these valuable synthons. The first example of an aldol reaction in the presence of a phosphine-borane adduct is also reported.

  DOI：

  10.1021/ol400381q
• 作为产物：
  描述：

  三异丙基氯硅烷 、 丙炔酸乙酯 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 以91%的产率得到ethyl 3-(triisopropylsilyl)propiolate
  参考文献：
  名称：

  Total Regio- and Diastereocontrol in the Aldol Reactions of Dienolborinates

  摘要：

  It is reported that appropriate dienolborinates can provide access to both diastereomers of 2-(hydroxymethyl)but-3-enoates through exclusive alpha-regiocontrol in a non-vinylogous pathway. Contrary to previous reports in which dialkylchloroboranes failed to enolize propanoates, acidity-enhanced but-3-enoates readily undergo enolization, offering unprecedented control over the formation of these valuable synthons. The first example of an aldol reaction in the presence of a phosphine-borane adduct is also reported.

  DOI：

  10.1021/ol400381q
• 作为试剂：
  描述：

  四氢呋喃 、 2,2,6,6-四甲基哌啶氧化物 在 氯化镍二甲氧基乙烷 、 4,4'-二叔丁基-2,2'-二吡啶 、 [Ir(dF(CF₃)ppy)₂(dtbbpy)](PF₆) 、 ethyl 3-(triisopropylsilyl)propiolate 作用下， 反应 20.08h， 以23%的产率得到2,2,6,6-tetramethyl-1-((tetrahydrofuran-2-yl)oxy)piperidine
  参考文献：
  名称：

  通过光氧化还原介导的Ni / Ir双催化对Ynone，Ynoate和Ynamide进行高度区域选择性和E / Z选择性加氢烷基化

  摘要：

  通过光氧化还原介导的Ni / Ir双重催化，高原子和步长经济性，实现了对酮，炔酸酯和炔酰胺的α-和高度E / Z选择性加氢烷基化反应，产生了三取代的烯酮，这是通用的合成原料。发达的反应选择性地递送了α/ Z异构体，这与先前报道的β-烷基化过程是互补的。三取代的烯酮可以通过后官能化转化为更有价值的化合物。

  DOI：

  10.1021/acs.orglett.8b02017

文献信息

• Palladium-Catalyzed Dehydrogenative Coupling Reaction of Terminal Alkynes with Unactivated Alkenes
  作者：Akira Yada、Shoki Nishi、Yuta Sato、Sakina Ichinoseki、Masahiro Murakami

  DOI：10.1002/jccs.201700268

  日期：2018.1

  Terminal alkynes having a bulky substituent dehydrogenatively couple with unactivated terminal alkenes with catalysis of palladium. The terminal sp carbon forms a bond with the internal sp2 carbon of the alkene regioselectively to produce branched, conjugated 1,3‐enynes with wide functional group tolerance.

  具有大取代基的末端炔烃在钯催化下与未活化的末端烯烃脱氢偶联。末端sp碳与烯烃的内部sp 2碳形成区域键，从而选择性地产生具有宽泛的官能团耐受性的支链共轭1,3-烯炔。
• Synthesis and Structure of Tetraarylcumulenes: Characterization of Bond-Length Alternation versus Molecule Length
  作者：Johanna A. Januszewski、Dominik Wendinger、Christian D. Methfessel、Frank Hampel、Rik R. Tykwinski

  DOI：10.1002/anie.201208058

  日期：2013.2.4

  BLA=0? Not so fast! A series of tetraarylcumulenes up to the length of a [9]cumulene has been synthesized and analyzed by X‐ray crystallography. The structural data show a distinct reduction in bond‐length alternation (BLA) as a function of molecule length, but this trend appears to reach a limit before a cumulenic structure with BLA=0 is achieved.

  BLA = 0？没那么快！X射线晶体学合成并分析了一系列直至[9]异丙苯的长度的四芳基枯烯。结构数据表明，键长交替（BLA）随分子长度的变化明显减少，但在达到BLA = 0的累积结构之前，这种趋势似乎已达到极限。
• Synthesis and Derivatization of Ethynyl α,α-Dibromomethyl Ketones:  Formation of Highly Functionalized Vinyl Triflates
  作者：Trent Rankin、Rik R. Tykwinski

  DOI：10.1021/ol027267i

  日期：2003.1.1

  [GRAPHICS]We describe the synthesis of alpha,alpha-dibromomethyl ynones (8) and their subsequent derivatization to vinyl acetates (10). These vinyl acetates feature a 1,1-dibromo-olefin moiety, which is readily exploited in palladium-catalyzed Sonogashira, Stille, and Suzuki cross-coupling reactions with alkynes, stannanes, and boronic acids, respectively. A novel one-pot process then directly converts the resulting vinyl acetates 11-13 to the vinyl triflate derivatives 14a-j.