dichloro(phenylethynyl)(vinyl)silane | 95598-23-5

• 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: dichloro(phenylethynyl)(vinyl)silane
• 英文别名: Dichloro-ethenyl-(2-phenylethynyl)silane
• CAS: 95598-23-5
• 化学式: C₁₀H₈Cl₂Si
• 分子量: 227.165
• InChiKey: SCYXIMGJFQNKFG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.22
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.0
• 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：

  dichloro(phenylethynyl)(vinyl)silane 在 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 为溶剂， 以74 %的产率得到ethenyl(2-phenylethynyl)silane
  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：

  苯乙炔 、 乙烯基三氯硅烷 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 以18 %的产率得到dichloro(phenylethynyl)(vinyl)silane
  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

文献信息

• Triethylborane: An “Old” Reagent with New Functions. 1,2-Hydroboration
  作者：Bernd Wrackmeyer、Ezzat Khan、Stefan Bayer、Khadija Shahid

  DOI：10.1515/znb-2007-0911

  日期：2007.9.1

  triethylborane, BEt3, can act as a hydroborating reagent. Thus, the reactions of BEt3 with alkyn-1-yl(trichloro)silanes, di(alkyn-1-yl)dichlorosilanes, alkyn- 1-yl(dichloro)vinylsilanes, trichloro(vinyl)silane, and dichloro(methyl)vinylsilane for several days in excess BEt3 as the solvent at 100 - 120 °C were found to give exclusively products of 1,2- hydroboration. This unexpected behaviour was compared

  与之前的发现相反，三乙基硼烷 BEt3 可以作为硼氢化试剂。因此，BEt3 与炔-1-基（三氯）硅烷、二（炔-1-基）二氯硅烷、炔-1-基（二氯）乙烯基硅烷、三氯（乙烯基）硅烷和二氯（甲基）乙烯基硅烷的反应发现在 100 - 120 °C 下使用过量的 BEt3 作为溶剂几天只产生 1,2-硼氢化反应的产物。这种意想不到的行为与类似反应中的三正丙基硼烷、BnPr3 和 9-硼双环 [3.3.1] 壬烷、9-BBN 的行为进行了比较，9-BBN 是一种完善的硼氢化试剂。所有产品均通过一组一致的 NMR 数据（1H、11B、13C 和 29Si NMR）进行表征。
• Reactions of stannyl carbamates with organochlorosilanes
  作者：N. V. Komarov、N. A. Ryzhkova、A. A. Andreev

  DOI：10.1007/bf00695833

  日期：1994.2

  Rapid and exothermic reactions of stannyl carbamates with organochlorosilanes result in cleavage of the Sn-O-C bond and afford silyl carbamates in a high yield.
• Koordinationsverhalten vinyl- und alkinylfunktionalisierter chlorsilane
  作者：Heinrich Lang、Markus Weinmann、Laszlo Zsolnai

  DOI：10.1016/0022-328x(96)06287-0

  日期：1996.9

  The coordination ability of vinyl and alkynyl substituted chlorosilanes of type (H2C=CH)(R)SiCl2 (1a R = Cl, Ib R = CH3, 1c R = C=CPh), (H2C=CH)(PhC=C)(R)SiCl [1d R = N(SiMe(3))(2), 1e R = C=CPh], as well as of the disiloxane [(H2C=CH)(PhC=C)(2)Si]O-2 (11) towards different organometallic compounds, such as Fe-2(CO)(9) (2), MnCp(CO)(3) (4, Cp = eta(5)-C5H5) and Co-2(CO)(8) (6) is discussed. Treatment of the vinylchlorosilanes 1a and 1b with Fe-2(CO)(9) (2) or MnCp(CO)(3) (4) in n-pentane or n-hexane produces the compounds [(eta(2)-H2C=CH)ML(n)](R)SiCl2 [3a ML(n) = Fe(CO)(4), R = Cl; 3b ML(n) = Fe(CO)(4), R = CH3; 5a ML(n) = MnCp(CO)(2), R = Cl; 5b ML(n) = MnCp(CO)(2), R = CH3] in which the vinyl unit is eta(2)-coordinated to an Fe(CO)(4) or MnCp(CO)(2) moiety. While compounds la or Ib do not react with Co-2(CO)(8) (6) under similar applied reaction conditions, it is found that the alkynyl substituted chlorosilanes 1c-1e yield on addition of Co-2(CO)(8) the complexes [(eta(2)-C=CPh)Co-2(Co)(6)](H2C=CH)(R)SiCl [7a R = Cl, 7b R = N(SiMe(3))(2), 7e R = C=CPh] or [(eta(2)-C=CPh)Co-2(CO)(6)](2)(H2C=CH)SiCl (7d) respectively. In these compounds, the phenylethinyl ligands are eta(2)-coordinated to a Co-2(CO)(6) fragment, thus forming bulky dicobalta-tetrahedrane units. Hydrolysis of compound 7c produces the disiloxane [(eta(2)-C=CPh)Co-2(CO)(6)](H2C=CH)(PhC=C)Si}O-2 (9). Additionally, this compound can be synthesized by the reaction of [(H2C=CH)(PhC=C)(2)Si]O-2 (11) with two equivalents of Co-2(CO)(8) (6). On treatment of 6 with one equivalent of the disiloxane 11 the formation of compound [(eta(2)-C=CPh)Co-2(CO)(6)](H2C=CH)(PhC=C)Si-O-Si(HC=CH2)(C=CPh)(2) (12) is obtained.All compounds were characterized by analytical and spectroscopic data (IR, H-1, C-13, Si-29 NMR, MS). The solid state structures of compounds [(eta(2)-C=CPh)Co-2(CO)(6)](H2C=CH)SiCl2 (7a) and [(eta(2)-C=CPh)Co-2(CO)(6)](H2C=CH)(PhC=C)SiCl (7c) are reported. Complexes 7a and 7c crystallize in the triclinic space group with the following cell parameters: 7a a = 816.8(3), b = 1597.5(9), c = 1601.5(8) pm, alpha = 101.49(4), beta = 100.01(4), gamma = 96.55(4)degrees, V = 2003(1) x 10(6) pm(3) and Z = 4; 7c a = 827.6(2), b = 914.0(2), c = 1696.7(5) pm, alpha = 89.35(2), beta = 76.75(2), gamma = 84.05(2)degrees, V = 1242(1) x 10(6) pm(3) and Z = 2.
• Catalytic Access to Diastereometrically Pure Four‐ and Five‐Membered Silyl‐Heterocycles Using Transborylation
  作者：Dominic R. Willcox、Emanuele Cocco、Gary S. Nichol、Stephen Thomas

  DOI：10.1002/anie.202401737

  日期：——

  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.