3-(trichlorosilyl)cyclohexene | 18139-74-7

• 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: 3-(trichlorosilyl)cyclohexene
• 英文别名: Trichloro-(cyclohex-2-enyl)silane；trichloro(cyclohex-2-en-1-yl)silane
• CAS: 18139-74-7
• 化学式: C₆H₉Cl₃Si
• 分子量: 215.582
• InChiKey: WPWUAANBFXQOJJ-UHFFFAOYSA-N

物化性质

• 沸点：
  202.4±29.0 °C(Predicted)
• 密度：
  1.24±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.75
• 重原子数：
  10
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 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：

  3-(trichlorosilyl)cyclohexene 在 正丁基锂 、 三苯基膦 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 190.0h， 生成 (E)-1-(2-(cyclohex-2-en-1-yldiethoxysilyl)phenyl)-2-phenyldiazene
  参考文献：
  名称：

  Intramolecular allylation of the azo group of 2-(allylsilyl)azobenzenes and its photocontrol

  摘要：

  Pentacoordinate allylsilanes bearing an azobenzene moiety were synthesized and their structures were elucidated. The reaction of allyldifluorosilane (E)-7a with BF3 center dot OEt2 did not proceed, but (E)-7a was allowed to react with a fluoride ion to give tetrafluorosilicate 8a via intramolecular allyl-migration from the silicon atom onto the azo group. Activation of both the nucleophilic and electrophilic parts by the Si center dot center dot center dot N interaction was found to be important for promotion of the allyl-migration reaction. The azobenzene moiety of the allylsilane was reversibly isomerized by photoirradiation. The (Z)-7a formed by photoirradiation of (E)-7a is in a tetracoordinate state in contrast to the (E)-7a, and it did not react with a fluoride ion at all under the conditions where (E)-7a reacted quantitatively. The reactivity was successfully controlled without changing any conditions other than the change of the coordination number of the silicon atom induced by photoirradiation. (c) 2006 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2006.08.045
• 作为产物：
  描述：

  1,3-环己二烯 在 bis(η3-allyl-μ-chloropalladium(II)) 、 三氯硅烷 、 三苯基膦 作用下， 反应 96.0h， 以93%的产率得到3-(trichlorosilyl)cyclohexene
  参考文献：
  名称：

  碳环核苷的新入口：环烯基硅烷与高价碘试剂介导的核碱基的氧化偶联反应。

  摘要：

  开发了一种合成碳环核苷的新方法。新的合成方法包括环烯基硅烷与高价碘试剂催化的甲硅烷基化核碱基的直接偶联反应。通过应用该方法，成功地合成了具有双（羟甲基）环己烯作为假糖部分的新型碳环胞苷衍生物，其被设计为潜在的抗HIV剂。

  DOI：

  10.1021/ol8012155

文献信息

• Silver-Catalyzed Asymmetric Sakurai−Hosomi Allylation of Ketones
  作者：Manabu Wadamoto、Hisashi Yamamoto

  DOI：10.1021/ja0553351

  日期：2005.10.1

  allylation of simple ketones. A significaant improvement of the reactivity was observed by using THF as the solvent. The catalyst turnover was increased by addition of 1 equiv of MeOH. AgF and (R)-DIFLUORPHOS predominantly formed a 1:1 complex that provided high enantioselectivity. This catalyst system can be applied to various simple ketones, and corresponding tertiary homoallylic alcohols were obtained

  AgF 和 (R)-DIFLUORPHOS 的复合物已被证明是简单酮不对称 Sakurai-Hosomi 烯丙基化的有效催化剂。通过使用 THF 作为溶剂，观察到反应性的显着提高。通过添加 1 当量的 MeOH 增加了催化剂的转化率。AgF 和 (R)-DIFLUORPHOS 主要形成 1:1 复合物，提供高对映选择性。该催化剂体系可应用于各种简单的酮类，得到相应的叔均烯丙醇，具有优异的对映选择性（高达96%ee）。从非环状和环状共轭酮中仅获得 1,2-加合物。还实现了区域选择性、非对映选择性和对映选择性巴豆化。E-或Z-巴豆基三甲氧基硅烷具有相似的非对映体比例和高对映选择性。
• Modification of Chiral Monodentate Phosphine Ligands (MOP) for Palladium-Catalyzed Asymmetric Hydrosilylation of Cyclic 1,3-Dienes
  作者：Tamio Hayashi、Jin Wook Han、Akira Takeda、Takeda Tang、Kenji Nohmi、Kotaro Mukaide、Hayato Tsuji、Yasuhiro Uozumi

  DOI：10.1002/1615-4169(20010330)343:3<279::aid-adsc279>3.0.co;2-5

  日期：2001.3.30

  Several MOP ligands 5 containing aryl groups at 2′ position of (R)-2-(diphenylphosphino)-1,1′-binaphthyl skeleton were prepared and used for palladium-catalyzed asymmetric hydrosilylation of cyclic 1,3-dienes 6 with trichlorosilane. Highest enantioselectivity was observed in the reaction of 1,3-cyclopentadiene (6a) catalyzed by a palladium complex (0.25 mol %) coordinated with (R)-2-(diphenylphosphino)-2′-(3

  制备了几个在（R）-2-（二苯基膦基）-1,1'-联萘骨架的2'位置含有芳基的MOP配体5，并将其用于钯催化的环1,3-二烯6与三氯硅烷的不对称氢化硅烷化。在与（R）-2-（二苯基膦基）-2'-（3,5-二甲基-4- ）配位的钯配合物（0.25 mol％）催化的1,3-环戊二烯（6a）反应中观察到最高的对映选择性甲氧基苯基）-1,1'-联萘基（5f），得到90％ee的（S）-3-（三氯甲硅烷基）环戊烯。
• Thermal reaction of cyclic alkadiene with trichlorosilane. Preparative and mechanistic aspects
  作者：Dong Eui Jung、Joon Soo Han、Bok Ryul Yoo

  DOI：10.1016/j.jorganchem.2012.10.015

  日期：2013.1

  reaction of cyclohexadienes with 1a under the same conditions gave a mixture of three hydrosilylation products such as 2-cyclohexenyltrichlorosilane (3b), 3-cyclohexenyltrichlorosilane (3c) and cyclohexyltrichlorosilane (5) in moderate yields, along with other unsaturated C6 components, such as benzene and cyclohexene. In the thermal reaction of cycloalkadienes with 1a, the five-membered-ring diene 2a undergoes

  研究了三氯硅烷（1a）与诸如环戊二烯（2a），1,3-环己二烯（2b）和1,4-环己二烯（2c）之类的环状链二烯在170°C至250°C的温度下的热反应。在该反应中，使用等摩尔比1a至2a，随着反应温度的升高，氢化硅烷化速率增加。的反应2A与1A在250℃，得到2- cyclopentenyltrichlorosilane（3A以良好的收率（82％）在1个小时内）作为主要氢化硅烷化产物。当使用二环戊二烯（2a'）代替2a。在相同条件下的大规模制备中，以82％的分离产率获得了3a。值得注意的是，可以将2a'用于氢化硅烷化，而在我们的热条件下不需要裂解步骤。在相同条件下环己二烯与1a的反应产生了三种氢化硅烷化产物的混合物，例如2-环己烯基三氯硅烷（3b），3-环己烯基三氯硅烷（3c）和环己基三氯硅烷（5），以及其他不饱和C6组分，如苯和环己烯。在环链二烯与1a的热反应中，五元环二烯2a与1a进行氢化硅烷化反应以及[4
• Palladium-Catalyzed Asymmetric Hydrosilylation of Cyclohexa-1,3-diene with Trichlorosilane by Use of Chiral Phosphoramidite Ligands from 3,3'-Disubstituted 1,1'-Binaphthols
  作者：Hyun-Sub Park、Hye Mi Shin、Suk Namgung、Jin Wook Han

  DOI：10.5012/bkcs.2014.35.9.2613

  日期：2014.9.20

  E-mail: [e-mail] May 1, 2014, Accepted May 20, 2014Key Words : Asymmetric catalysis, Hydrosilylation, Palladium, Chiral phosphoramidites, AllylsilaneSince a breakthrough enhancing catalytic activity andenantioselectivity by use of axially chiral monophosphineligands (MOP) was reported in the hydrosilylation of 1-octene,

  E-mail: [e-mail] 2014 年 5 月 1 日接收，2014 年 5 月 20 日接受 关键词：不对称催化、氢化硅烷化、钯、手性亚磷酰胺、烯丙基硅烷报道了 1-辛烯的氢化硅烷化，
• Facile and Highly Stereoselective Synthesis of Homoallylic Alcohols Using Organosilicon Intermediates
  作者：Shu Kobayashi、Koichi Nishio

  DOI：10.1021/jo00101a021

  日期：1994.11

  Allyltrichlorosilanes regioselectively reacted with aldehydes in N,N-dimethylformamide (DMF) without a catalyst to afford the corresponding homoallylic alcohols in high yields. The reactions proceeded under neutral conditions, and syn- and anti-homoallylic alcohols were stereoselectively obtained from (Z)- and (E)-allyltrichlorosilanes, respectively. In these reactions, DMF coordinated to the silicon atom of the allyltrichlorosilanes to form hypervalent silicates, which in turn reacted with aldehydes smoothly. Solvent effects in these reactions were also examined. The reactions were applied to the one-pot synthesis of homoallylic alcohols from allylic chlorides via organosilicon intermediates. While syn-homoallylic alcohols were prepared from (Z)-allyl chlorides, antihomoallylic alcohols were obtained from (E)-allyl chlorides. Unique regioselectivities in the reactions of 1-chloro-2,4-pentadiene were also found. Finally, the one-pot synthesis of homoallylic alcohols from 1,3-dienes is reported.