5-hexen-1-ynyltrimethylsilane | 1578-50-3

• 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: 5-hexen-1-ynyltrimethylsilane
• 英文别名: (hex-5-en-1-ynyl)trimethylsilane；(hex-5-en-1-yn-1-yl)trimethylsilane；1-Trimethylsilyl-hex-5-en-1-in；Hex-5-en-1-ynyl(trimethyl)silane
• CAS: 1578-50-3
• 化学式: C₉H₁₆Si
• mdl: MFCD11553881
• 分子量: 152.312
• InChiKey: HLZYISUMIDAZQW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  10
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.555
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  5-hexen-1-ynyltrimethylsilane 、 水 以80%的产率得到
  参考文献：
  名称：

  MILLER, J. A.;NEGISHI, EI-ICHI, ISRAEL J. CHEM., 1984, 24, N 2, 76-81

  摘要：

  DOI：
• 作为产物：
  描述：

  hexa-1,5-diyn-1-yltrimethylsilane 在 Lindlar's catalyst 氢气 作用下， 以 甲醇 为溶剂， 生成 5-hexen-1-ynyltrimethylsilane
  参考文献：
  名称：

  Forost,M.P. et al., Journal of general chemistry of the USSR, 1965, vol. 35, p. 708 - 713

  摘要：

  DOI：

文献信息

• Electrophilic Cyclization of Aryldiacetylenes in the Synthesis of Functionalized Enediynes Fused to a Heterocyclic Core
  作者：N. A. Danilkina、A. E. Kulyashova、A. F. Khlebnikov、S. Bräse、I. A. Balova

  DOI：10.1021/jo501396s

  日期：2014.10.3

  variety of asymmetrically substituted acyclic enediynes fused to heterocycles. The tolerance of the developed methodology to a variety of functional groups is a great advantage in the synthesis of macrocyclic enediyne systems fused to a heterocyclic core. Synthesis of indole-fused 12-membered macrocyclic dienediyne was achieved using ring-closing metathesis as a key step.

  开发了一种有效的策略，用于合成与苯并噻吩，苯并呋喃和吲哚稠合的不对称取代烯二炔。所提出的方法基于联乙炔的亲电环化和Sonogashira偶联。因此，易得邻位的碘环化-官能化的（buta-1,3-diynyl）芳烃被用作合成2-ethynyl-3-iodoheteroindeness的直接方法。这些底物及其修饰的衍生物很容易通过Sonogashira与乙炔的偶合转化为稠合到杂环上的各种不对称取代的无环烯二炔。所开发的方法对各种官能团的耐受性是在稠合至杂环核心的大环烯二炔系统合成中的巨大优势。以闭环复分解为关键步骤，完成了吲哚稠合的12元大环二烯二炔的合成。
• Ring-Closing Metathesis of Co₂(CO)₆–Alkyne Complexes for the Synthesis of 11-Membered Dienediynes: Overcoming Thermodynamic Barriers
  作者：Natalia A. Danilkina、Anna G. Lyapunova、Alexander F. Khlebnikov、Galina L. Starova、Stefan Bräse、Irina A. Balova

  DOI：10.1021/acs.joc.5b00409

  日期：2015.6.5

  The feasibility of ring-closing metathesis (RCM) as a synthetic entry to 10- and 11-membered dienediynes fused to a benzothiophene core was explored by experimental and theoretical investigations. An established sequence of iodocyclization of o-(buta-1,3-diynyl)thioanisoles followed by Sonogashira coupling to form diethynylbenzothiophenes was used to synthesize terminal benzothiophene-fused enediyne

  通过实验和理论研究探索了闭环复分解（RCM）作为10和11元二烯二炔与苯并噻吩核融合的合成入口的可行性。o的碘环化的既定序列使用-（buta-1,3-diynyl）thioanisoles，然后通过Sonogashira偶联形成二乙炔基苯并噻吩，以合成末端苯并噻吩稠合的二炔二烯烃作为RCM的底物。由于在标准RCM条件下这些底物的反应性出乎意料的缺乏，我们应用DFT计算来揭示根本原因是吉布斯自由能的正变化。当提供小于12元的环时，还发现吉布斯自由能的变化对于吲哚和苯甲酸酯化的末端二烯烃的RCM是正的。我们发现烯二炔-二烯烃底物的修饰形式为Co 2（CO）6–炔烃配合物允许通过RCM获得目标苯并噻吩稠合的11元二烯二炔；因此，炔烃络合策略提供了一种有效的技术来克服此类大环化的挑战。
• Formation of 2-[1-(Trimethylsilyl)alkylidene]-4-cyclopentene-1,3-dione from Lewis Acid-Catalyzed Reaction of Cyclobutenedione Monoacetal with Alkynylsilane:  Novel Cationic 1,2-Silyl Migrative Ring Opening and Subsequent 5-<i>Exo</i>-<i>Trig</i> Ring Closure
  作者：Yoshihiko Yamamoto、Masashi Noda、Masatomi Ohno、Shoji Eguchi

  DOI：10.1021/jo961552w

  日期：1997.3.1

  An ethoxycarbenium ion intermediate, which was produced by the catalytic action of a Lewis acid on a cyclobutenedione monoacetal, reacted with phenyl(trimethylsilyl)acetylene to give a normal electrophilic substitution product. In sharp contrast, the same catalytic reaction with bis(trimethylsilyl)acetylene afforded a 2-methylene-4-cyclopentene-1,3-dione derivative as a ring expansion product instead of an alkynylation product. Butyl(trimethylsilyl)acetylene showed reactivity between the aforementioned compounds as a result of the formation of both types of products. In the reactions of such alkyl-substituted silylacetylenes, both E- and Z-isomers of 2-(1-silylalkylidene)cyclopentenediones were obtained in ratios dependent on the reaction temperature and the amount of Lewis acid. This rearrangement resulted from unprecedented cationic 1,2-silyl migration on the alkynylsilane and subsequent ring expansion promoted by the formed vinyl cation intermediate. A detailed mechanism of the novel ring-expansion route is discussed with the aid of PM3 calculations, especially for the reclosure step, which is explained by a 5-exo-trig cyclization rather than a pentadienyl cation electrocyclization.
• A preparation of vinylsilanes and vinyl halides containing alkene or epoxide functional groups
  作者：Paul E. Peterson、David J. Nelson、Rick Risener

  DOI：10.1021/jo00362a041

  日期：1986.6
• PETERSON, P. E.;NELSON, D. J.;RISENER, R., J. ORG. CHEM., 1986, 51, N 12, 2381-2382
  作者：PETERSON, P. E.、NELSON, D. J.、RISENER, R.

  DOI：——

  日期：——