dimethyl(phenylethynyl)(vinyl)silane | 177651-95-5

• 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: dimethyl(phenylethynyl)(vinyl)silane
• 英文别名: Ethenyl-dimethyl-(2-phenylethynyl)silane
• CAS: 177651-95-5
• 化学式: C₁₂H₁₄Si
• 分子量: 186.329
• InChiKey: OJJFXSBQJYOUKJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.01
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.17
• 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：

  dimethyl(phenylethynyl)(vinyl)silane 以 氘代苯 为溶剂， 反应 16.17h， 生成 1,1-dimethyl-5-phenyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2,3-dihydrosilole
  参考文献：
  名称：

  Catalytic Access to Diastereometrically Pure Four‐ and Five‐Membered Silyl‐Heterocycles Using Transborylation

  摘要：

  Silyl‐heterocycles offer a unique handle to expand and explore chemical space, reactivity, and functionality. The shortage of catalytic methods for the preparation of diverse and functionalized silyl‐heterocycles however limits widespread exploration and exploitation. Herein the borane‐catalyzed intramolecular 1,1‐carboboration of silyl‐alkynes has been developed for the synthesis of 2,3‐dihydrosilolyl and silylcyclobut‐2‐enyl boronic esters. Successful, catalytic carboboration has been achieved on a variety of functionally diverse silyl‐alkynes, using a borane catalyst and transborylation enabled turnover. Mechanistic studies, including 13C‐labelling, computational studies, and single‐turnover experiments, suggest a reaction pathway proceeding by 1,2‐hydroboration, 1,1‐carboboration, and transborylation to release the alkenyl boronic ester product and regenerate the borane catalyst.

  DOI：

  10.1002/anie.202401737
• 作为产物：
  描述：

  在 copper(l) chloride 、 三环己基膦 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 6.0h， 以36.5 mg的产率得到dimethyl(phenylethynyl)(vinyl)silane
  参考文献：
  名称：

  烷基炔基硅酸酯催化脱羧成炔基硅烷

  摘要：

  在这里，我们描述了一种用于制备炔基硅烷的脱羧方法。在催化量的CuCl和PCy 3的存在下，于80°C在N，N-二甲基甲酰胺（DMF）中处理炔基硅烷基酯，可以以优异的产率得到相应的炔基硅烷。铜催化的脱羧反应在温和的反应条件下以较低的催化剂负载量（0.5 mol％的CuCl和1.0 mol％的PCy 3）平稳进行，并且易于扩展至克量。

  DOI：

  10.1021/acs.organomet.0c00433

文献信息

• Iridium-Promoted Conversion of Chlorosilanes to Alkynyl Derivatives in a One-Pot Reaction Sequence
  作者：Ireneusz Kownacki、Bartosz Orwat、Bogdan Marciniec

  DOI：10.1021/om500320t

  日期：2014.6.23

  in the synthesis of silyl-functionalized alkynes via silylative coupling of terminal alkynes/diynes with iodosilanes, we propose a new protocol allowing employment of various mono- and dichlorosilanes as reagents. The process is based on a sequence of two reactions occurring simultaneously: i.e., conversion of initial chlorosilane (SiR1nCl4–n) to the appropriate iodosilane via Cl/I nucleophilic substitution

  通过利用铱系统[的Ir（μ-Cl）的（CO）的催化潜力的2 } 2 ] / NET（我-Pr）2通过末端炔烃/二炔的silylative耦合在甲硅烷基官能炔烃的合成与iodosilanes，我们提出了一个新的协议，允许各种单和二氯硅烷作为试剂的就业机会。该过程是基于同时出现两种反应的序列：即初始氯硅烷的转化率（SIR 1 ñ氯-4- Ñ）到地经由Cl适当iodosilane / I的亲核取代和其进一步转化为silylalkyne衍生物（（SIR 1 ñ（C≡CR 2）4-Ñ）通过铱-催化的与末端炔silylative耦合。在最佳条件下，该方法已被证明是在广泛的氯硅烷的一种丰富的各种相应的炔基官能化的硅衍生物的组合的转化有效和通用性。另外，明确限定的铱（I）的炔前体与Me中等摩尔反应的NMR研究3的Si-I显示，≡Si-I键活化在iodosilane分子通过氧化除铱中心发生。
• Et2Zn-mediated stoichiometric C(sp)-H silylation of 1-alkynes and chlorosilanes
  作者：Pan Huang、Dawen Xu、Robert M. Reich、Felix Kaiser、Boping Liu、Fritz E. Kühn

  DOI：10.1016/j.tetlet.2019.05.017

  日期：2019.6

  series of functional groups are tolerated in this reaction. Mechanistic studies support Zn alkynilides as intermediates in the reaction. This reaction protocol provides a practical method for the preparation of alkynylsilanes and expands the application of organometallic zinc in organic synthesis.

  报道了Et 2 Zn介导的1-炔烃甲硅烷基化的第一个例子。在该反应中容许一系列官能团。机理研究支持炔基锌作为反应的中间体。该反应方案为制备炔基硅烷提供了一种实用的方法，并扩展了有机金属锌在有机合成中的应用。
• A Convenient Synthesis of Alkynylsilanes by Silylation of Copper(I) Alkynides
  作者：Hikaru Sugita、Yasuo Hatanaka、Tamejiro Hiyama

  DOI：10.1246/cl.1996.379

  日期：1996.5

  Alkynylation of chlorosilanes with copper(I) alkynides takes place smoothly in the presence of triphenylphosphine, N, N, N′, N′-tetramethylethylenediamine, or zinc powder to give a variety of alkynylsilanes in good yields.

  在三苯基膦、N、N、N'、N'-四甲基乙二胺或锌粉的存在下，氯硅烷与铜（I）炔化物的炔基化反应顺利进行，以良好的产率得到各种炔基硅烷。
• An efficient route to substituted 1-silacyclopent-2-enes and 1-silacyclohex-2-enes via consecutive 1,2-hydroboration and 1,1-organoboration
  作者：Bernd Wrackmeyer、Oleg L. Tok、Rhett Kempe

  DOI：10.1016/j.ica.2005.03.016

  日期：2005.11

  The reaction of alkyn-1-yl(vinyl)silanes R2Si(C CR1)CH=CH2[R = Me (1), Ph (2); R-1 = Bu-t (a), Ph (b), SiMe3 (c)] with 9-borabicyclo[3.3.1]nonane in a 1:1 ratio affords the 1-silacyclopent-2-ene derivatives 4a-c (R = Me) and 5a-c (R = Ph) as a result of selective intermolecular 1,2-hydroboration. of the vinyl group, followed by intramolecular 1, 1-organoboration of the alkynyl substituent. The analogous reaction sequence converts the alkyn-1-yl(allyl)dimethylsilanes 3a,c into the 1-silacyclohex-2-ene derivatives 7a,c. All reactions were monitored by Si-29 NMR spectroscopy and the structural assignment of the final products was based on multinuclear magnetic resonance data (H-1, B-11, C-13 and Si-29 NMR). The molecular structure of 6a was determined by X-ray analysis. (c) 2005 Elsevier B.V. All rights reserved.
• JP2022/59855
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