allyl-dimethyl-vinylsilane | 22146-25-4

• 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: allyl-dimethyl-vinylsilane
• 英文别名: Allyldimethyl(vinyl)silane；ethenyl-dimethyl-prop-2-enylsilane
• CAS: 22146-25-4
• 化学式: C₇H₁₄Si
• 分子量: 126.274
• InChiKey: XYYDRQRUUNENNH-UHFFFAOYSA-N

物化性质

• 沸点：
  108-109 °C
• 密度：
  0.742±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.61
• 重原子数：
  8
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.43
• 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：

  allyl-dimethyl-vinylsilane 在 氨 作用下， 以 乙醇 为溶剂， 反应 5.0h， 生成 3,3-dimethyl-3-sila-1-hexene-6-thiol
  参考文献：
  名称：

  6-Exo and 7-endo photocyclization of αβ-unsaturated organosilicon ω-thiols

  摘要：

  The regioselectivity of cyclization of 3,3- and 4,4-dimethylsila-1-hexene-6-thiols upon UV-irradiation is reported. Ring closure involving the vinyl group at silicon results in the preferred formation of the exo-cyclic product, whereas a high and reversed regio- selectivity is observed when the cyclization reaction occurs via the allyl group at silicon.

  DOI：

  10.1016/s0040-4039(00)79255-0
• 作为产物：
  描述：

  二甲基乙烯基氯硅烷 、 氯丙烯镁 在 3-氯丙烯 作用下， 以 四氢呋喃 为溶剂， 反应 3.0h， 以71.5%的产率得到allyl-dimethyl-vinylsilane
  参考文献：
  名称：

  Zhun', V.I.; Tsvetkov, A. L.; Sheludyakov, V. D., Journal of general chemistry of the USSR, 1988, vol. 58, # 7, p. 1425 - 1431

  摘要：

  DOI：

文献信息

• Regioselective Carboxylation of Silicon-Stabilized Allylic Carbanions and the Synthetic Utility of 2-Silyl-3-butenoates
  作者：Hidemitsu Uno

  DOI：10.1246/bcsj.59.2471

  日期：1986.8

  Carbanions of allylic dimethylphenylsilanes show remarkable regioselectivity toward both carboxylation with carbon dioxide and methylation with methyl iodide. Methylation of these compounds occurred preferentialy at α position, although allyltrimethylsilane and allyltriphenylsilane are known to give γ selectivity toward the same electrophiles. Moreover, their aluminum “ate” complexes react with carbon

  烯丙基二甲基苯基硅烷的碳负离子对二氧化碳的羧化和甲基碘的甲基化都显示出显着的区域选择性。这些化合物的甲基化优先发生在 α 位，尽管已知烯丙基三甲基硅烷和烯丙基三苯基硅烷对相同的亲电试剂具有 γ 选择性。此外，它们的铝“ate”复合物在 a 位置与二氧化碳发生区域选择性反应，而与烯丙基部分的甲基取代模式无关。α-羧化烯丙基硅烷被证明是酯化后 3-（甲氧基羰基）烯丙基阴离子的有用合成子。
• Diastereoselective Cyclization of 1,5-Dienes with the C−H Bond of Pyridine Catalyzed by a Cationic Mono(phosphinoamide) Alkyl Scandium Complex
  作者：Yanhui Chen、Di Song、Jing Li、Xiaoyan Hu、Xianjia Bi、Tao Jiang、Zhaomin Hou

  DOI：10.1002/cctc.201700980

  日期：2018.1.9

  The carbocyclization of non‐conjugated dienes mediated by organometallics is an important reaction for the synthesis of a variety of carbocyclic derivatives, but the direct annulation of dienes with an inert C−H bond of a substrate has remained unexplored to date. We herein report a series of novel rare‐earth dialkyl complexes bearing a phosphinoamide anion and demonstrate that the combination of a

  有机金属介导的非共轭二烯的碳环化是合成各种碳环衍生物的重要反应，但是迄今为止，具有底物惰性CH键的二烯直接环化尚未得到探索。本文我们报告了一系列新颖的稀土类的二烷基配合物带有phosphinoamide阴离子的并证明单（phosphinoamido）的组合-ligated钪二烷基与B（C复杂6 ˚F 5）3次的结果中的一种极好的催化剂顺式- 1,5-二烯与邻-C的选择性环化（sp 2）-吡啶的H键可提供一个新的吡啶基官能化的1,3-二取代的环戊烷衍生物家族，该衍生物含有单环，双环，螺环和杂环骨架，具有中等至优异的收率，具有高非对映选择性（顺式/反式可达99：1） 。
• Efficient Generation of<i>ortho</i>-Naphthoquinone Methides from 1,4-Epoxy-1,4-dihydronaphthalenes and Their Annulation with Allyl Silanes
  作者：Yoshinari Sawama、Yuko Shishido、Takayoshi Yanase、Koichi Kawamoto、Ryota Goto、Yasunari Monguchi、Yasuyuki Kita、Hironao Sajiki

  DOI：10.1002/anie.201207315

  日期：2013.1.28

  dihydronaphthopyran derivatives were obtained in good yield by the regio‐ and stereoselective annulation of ortho‐naphthoquinone methides with allyl silanes. The ortho‐naphthoquinone methides were generated in situ from 1‐siloxymethyl‐1,4‐epoxy‐1,4‐dihydronaphthalenes under FeCl3 catalysis (see scheme; allyl‐TMS=allyltrimethylsilane, TBS=tert‐butyldimethylsilyl, TMS=trimethylsilyl).

  通过邻-萘醌甲基化物与烯丙基硅烷的区域和立体选择性环化，可得到高收率的药学上有用的二氢萘并吡喃衍生物。的邻位从原位产生-naphthoquinone甲基化物1-甲硅烷氧基-1,4-环氧-1,4-二氢萘下的FeCl 3催化（参见方案;烯丙基TMS =烯丙基三甲基硅烷，TBS =叔丁基二，TMS =三甲基甲硅烷）。
• Rh(I)-Catalyzed Dehydrogenative Silylation of Divinylsilanes with Dimethylphenylsilane
  作者：Yukio Kawanami、Keiji Yamamoto

  DOI：10.1246/bcsj.69.1117

  日期：1996.4

  Rh(I)-catalyzed dehydrogenative silylation was selectively carried out by using divinylsilanes and half an equimolar amount of trialkylsilanes under ambient conditions to give 1,2-disilylethene and ethylvinylsilane derivatives in equimolar amounts. The mechanistic aspects for the dehydrogenative silylation were discussed in terms of the consecutive migratory insertions of the alkene moiety into both Rh–Si and Rh–H bonds which are formed by an oxidative addition of the hydrosilane to the Rh(I) catalyst precursor.

  在环境条件下，使用二乙烯基硅烷和一半等摩尔量的三烷基硅烷，选择性地进行了 Rh（I）催化的脱氢硅烷化反应，得到了等摩尔量的 1,2-二硅烷和乙烯基硅烷衍生物。讨论了脱氢硅烷化的机理，即通过氢硅烷与 Rh(I) 催化剂前体的氧化加成，将烯基连续迁移插入到 Rh-Si 和 Rh-H 键中。
• Regioselective Hydroalkylation of Vinyl- and Allylsilanes as Well as Vinylgermanes under Ni–H Catalysis
  作者：Daniel Brösamlen、Martin Oestreich

  DOI：10.1021/acs.orglett.3c01881

  日期：2023.7.21

  A Ni–H-catalyzed hydroalkylation of vinylsilanes and -germanes as well as allylsilanes with unactivated alkyl iodides is reported. Unlike related reactions of styrene or vinyl boronate esters, the addition across the C–C double bond proceeds with anti-Markovnikov selectivity to deliver the linear regioisomer. Mechanistic control experiments support a radical mechanism, and a competition experiment

  报道了乙烯基硅烷和α-锗烷以及烯丙基硅烷与未活化的烷基碘的 Ni-H 催化加氢烷基化反应。与苯乙烯或乙烯基硼酸酯的相关反应不同，C-C 双键上的加成反应具有反马尔可夫尼科夫选择性，从而产生线性区域异构体。机械控制实验支持一种激进的机制，而竞争实验表明，化学选择性有利于乙烯基而不是烯丙基。