(α-bromovinyl)dimethylchlorosilane | 72425-77-5

• 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: (α-bromovinyl)dimethylchlorosilane
• 英文别名: (1-bromovinyl)chlorodimethylsilane；(1-bromovinyl)dimethylchlorosilane；1-Bromovinyldimethylsilyl chloride；(bromovinyl)chlorodimethylsilane；1-Bromoethenyl-chloro-dimethylsilane
• CAS: 72425-77-5
• 化学式: C₄H₈BrClSi
• 分子量: 199.55
• InChiKey: PANVQUHCSFALQJ-UHFFFAOYSA-N

物化性质

• 沸点：
  80 °C(Press: 120 Torr)
• 密度：
  1.332±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.88
• 重原子数：
  7
• 可旋转键数：
  1
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 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：

  (α-bromovinyl)dimethylchlorosilane 在 喹啉 作用下， 生成 ethynyldimethylchlorosilane
  参考文献：
  名称：

  VICINAL DEHYDROBROMINATION OF (α-BROMOVINYL)CHLOROSILANES WITH QUINOLINE. A NEW ROUTE TO ETHYNYLCHLOROSILANES

  摘要：

  (研究发现，CH2=CBrSiRnCl3-n（R = Me, Et; n = 0, 1, 2）型（α-溴乙烯基）氯硅烷与喹啉进行脱溴反应，可生成相应的乙炔基氯硅烷。

  DOI：

  10.1246/cl.1979.1287
• 作为产物：
  描述：

  二甲基乙烯基氯硅烷 在 溴 作用下， 反应 0.25h， 以58.4%的产率得到(α-bromovinyl)dimethylchlorosilane
  参考文献：
  名称：

  将烯烃转化为卡宾的热诱导 1,2-转变：硅能做到吗？如果是，为什么不是碳？

  摘要：

  通过实验和理论研究了通过 1,2-甲硅烷基转移将烯烃热异构化为卡宾。对于无环乙烯基硅烷，没有发现这种重排的证据，也无法在顺式、反式异构化中识别出硅的电子辅助。2,4-二甲基-1, 3-二硅杂环丁烷的偶然合成允许对其气相热环膨胀进行动力学检查，以生成 2-亚甲基-1,3-二硅杂环戊烯。Arrhenius 参数（log A = 12.48，E{sub act} = 54.09 kcal/mol）是第一个报告的烯烃到卡宾重排的参数。类似的全碳系统未能环扩。Ab initio 计算表明，这与根据环应变考虑做出的任何预测相反。计算表明，对于甲硅烷基迁移，过渡态较晚，实际上是卡宾，而对于碳迁移，TS 较早且能量比所得卡宾高得多。重新检查了 2-亚甲基-1-硅杂环丁烷重排，发现在低于通过卡宾 TS 扩环所需的温度下发生 1,4-双基的可逆开环。45 个参考文献，5 个图，1 个标签。

  DOI：

  10.1021/ja00152a010
• 作为试剂：
  描述：

  (S)-1,1-dibenzyl-2-(3-(tert-butyldimethylsilyloxy)butylidene)hydrazine 在 四丁基氟化铵 、 (α-bromovinyl)dimethylchlorosilane 、 三乙胺 作用下， 生成 (E)-1,1-dibenzyl-2-(but-2-enylidene)hydrazine
  参考文献：
  名称：

  Enhanced reactivity in radical cyclizations of hydrazones using the silicon-tethered 1-bromovinyl group

  摘要：

  A silicon-tethered 1-bromovinyl group was shown to function as a radical precursor for tin-mediated vinyl additions to chiral alpha- or beta-hydroxyhydrazone. In contrast to related thiyl-mediated methods, these vinyl bromides were not limited to the 5-exo cyclization mode. A series of Si-tethered 5-exo and 6-exo cyclizations formed the corresponding five- and six-membered exo-methylene- substituted oxasilacycles. Treatment with fluoride cleaved the Si-C and Si-O bonds to afford the corresponding allylic hydrazines. Diastereoselectivities ranged from 2:1 to 25:1 (anti:syn) for the 5-exo cyclizations, depending on the size of the exocyclic substituent, but 6-exo cyclization was not diastereoselective. A variant involving Tamao oxidation of the exo-methylene oxasilacyclopentane intermediate afforded a methyl ketone, a net process corresponding to addition of a radical acyl anion equivalent. (C) 2007 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2007.03.017

文献信息

• Extension to the Silyl-Tethered Radical Cyclization: Cyclohex-2-en-1-oxy Vinyl Silanes in Stereoselective Radical Addition/Cyclization Cascades
  作者：Andrey A. Mikhaylov、Samir Z. Zard

  DOI：10.1021/acs.orglett.7b00627

  日期：2017.4.7

  A novel radical cascade reaction of xanthates with 1-[(vinyldimethylsilyl)oxy]cyclohex-2-enes is developed. Due to the steric and electronic differentiation of the two olefinic functions, exclusive regioselectivity and high stereoselectivity of the addition–cyclization are observed. Several methods for modification of both the silicon tether and the xanthate function are reported.

  提出了黄原酸酯与1-[（（乙烯基二甲基甲硅烷基）氧基]环己-2-烯的自由基自由基级联反应的新方法。由于两个烯烃功能的空间和电子差异，可以观察到加成环化的排他区域选择性和高立体选择性。报道了几种同时修饰硅系链和黄药功能的方法。
• Divergent Synthesis of Scabrolide A and Havellockate via an exo-exo-endo Radical Cascade
  作者：Chen Peng、Quanping Guo、Guo-Xiong Xu、Luqiong Huo、Weilin Wu、Tian-Yi Chen、Xin Hong、Pengfei Hu

  DOI：10.1021/jacs.4c03995

  日期：2024.5.29

  Here we report a concise and divergent synthesis of scabrolide A and havellockate, representative members of polycyclic marine natural product furano(nor)cembranoids. The synthesis features a highly efficient exo-exo-endo radical cascade. Through the generation of two rings, three C–C bonds, and three contiguous stereocenters in one step, this remarkable transformation not only assembles the bowl-shaped

  在这里，我们报告了多环海洋天然产物呋喃（正）西松烷内酯的代表成员scabrolide A和havellockate的简明而发散的合成。该合成具有高效的外-外-内自由基级联反应。通过一步生成两个环、三个 C-C 键和三个连续的立构中心，这一非凡的转变不仅从简单的构建单元组装出碗形的常见 6-5-5 稠合环系统，而且还精确地安装了功能在所需的位置，并为进一步不同的制备两个目标分子奠定了基础。进一步的研究表明，级联中稳健且不寻常的 6-内基自由基加成可能是由底物的刚性促进的。
• Radical hydrogen abstraction–cyclization with a 2-bromovinylsilyl group as a bifunctional tether
  作者：Makoto Sukeda、Akira Matsuda、Satoshi Shuto

  DOI：10.1016/j.tet.2005.06.021

  日期：2005.8

  In order to develop an efficient method for the regio- and stereoselective introduction of a carbon substituent, a radical hydrogen abstraction-cyclization using 1- and 2-bromovinylsilyl groups as bifunctional tethers was studied. Although, the selective introduction of a carbon substituent at the position P to the hydroxyl was unsuccessful, a carbon substituent was introduced with the 2-bromovinylsilyl ethers via a hydrogen abstraction-cyclization. These reactions were analyzed based on the bond dissociation energies obtained by theoretical calculations. (c) 2005 Elsevier Ltd. All rights reserved.
• 1-Silylvinyl radical cyclization: silicon-mediated regio- and stereoselective hydroacylation and hydrovinylation of allyl alcohols
  作者：Kohei Tamao、Kimio Maeda、Takashi Yamaguchi、Yoshihiko Ito

  DOI：10.1021/ja00195a065

  日期：1989.6
• MATSUMOTO HIDEYUKI; KATO TAKAYUKI; MATSUBARA IKUYA; HOSHINO YOSHIKAZU; NA+, CHEM. LETT., 1979, NO 10, 1287-1290
  作者：MATSUMOTO HIDEYUKI、 KATO TAKAYUKI、 MATSUBARA IKUYA、 HOSHINO YOSHIKAZU、 NA+

  DOI：——

  日期：——