trichloro((S)-cyclohex-2-enyl)silane | 38053-77-9

• 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: trichloro((S)-cyclohex-2-enyl)silane
• 英文别名: (S)-3-(trichlorosilyl)cyclohexene；(S)-3-trichlorosilylcyclohexene；(s)-Trichloro(cyclohex-2-enyl)silane；trichloro-[(1S)-cyclohex-2-en-1-yl]silane
• CAS: 38053-77-9
• 化学式: C₆H₉Cl₃Si
• 分子量: 215.582
• InChiKey: WPWUAANBFXQOJJ-ZCFIWIBFSA-N

物化性质

• 沸点：
  87-90 °C(Press: 17 Torr)
• 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 、 trichloro((S)-cyclohex-2-enyl)silane 在 水 作用下， 以 四氢呋喃 为溶剂， 反应 18.0h， 以74%的产率得到((S)-cyclohex-2-enyl)trimethylsilane
  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
• 作为产物：
  描述：

  1,3-环己二烯 在 bis(η3-allyl-μ-chloropalladium(II)) 、 (R)-Ph₂P-(Me₂-MeOC₆H₂)-Oct₂-binaphthyl 三氯硅烷 作用下， 反应 168.0h， 生成 trichloro((S)-cyclohex-2-enyl)silane 、 (R)-trichloro(cyclohex-2-enyl)silane
  参考文献：
  名称：

  含长链烷基的新型 MOP 配体的制备及其在钯催化环状 1,3-二烯不对称氢化硅烷化中的应用

  摘要：

  制备了一种在 (R)-2-(二苯基膦基)-2'-芳基-1,1'-联萘骨架的 6 和 6' 位含有正辛基的新型 MOP 配体，并将其用于钯催化的环状不对称氢化硅烷化反应。 1,3-二烯与三氯硅烷。通过引入正辛基，钯-膦催化剂在反应体系中变得可溶，在低反应温度下实现了高催化活性。

  DOI：

  10.1246/cl.2001.976

文献信息

• 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。
• 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，
• Enhanced catalytic activity in asymmetric hydrosilylation of 1,3-dienes with a soluble palladium catalyst
  作者：Jin Wook Han、Tamio Hayashi

  DOI：10.1016/s0957-4166(02)00094-0

  日期：2002.3

  A new MOP ligand 8 containing two it-octyl groups at the 6 and 6' positions of the (R)-2-(diphenylphosphino)-2'-aryl-1,1'-binaphthyl skeleton was prepared and used for the palladium-catalyzed asymmetric hydrosilylation of 1,3-dienes with trichlorosilane. The introduction of the n-octyl groups made the palladium-phosphine catalyst soluble in the reaction system, realizing high catalytic activity at a low reaction temperature. As a result, ligand 8 showed highest enantioselectivity for both cyclic and linear 1,3-dienes. (C) 2002 Elsevier Science Ltd. All rights reserved.
• Asymmetric hydrosilylation of cyclohexa-1,3-diene with trichlorosilane by palladium catalysts coordinated with chiral phosphoramidite ligands
  作者：Hoon Seo Park、Jin Wook Han、Ryo Shintani、Tamio Hayashi

  DOI：10.1016/j.tetasy.2013.02.002

  日期：2013.4

  Chiral phosphoramidite ligands prepared from (S)-binaphthol and various secondary amines were examined for the palladium-catalyzed asymmetric hydrosilylation of cyclohexa-1,3-diene with trichlorosilane. With a sterically demanding phosphoramidite bearing bis(diphenylmethyl)amine, the high enantiomeric excess of 87% was achieved, which is the highest enantioselectivity in the hydrosilylation of cyclohexadiene reported to date. The catalytic activity in the present hydrosilylation was high with all of the ligands employed, while the enantioselectivities varied dramatically depending on the dialkylamine moiety of the phosphoramidite ligand. (c) 2013 Elsevier Ltd. All rights reserved.
• A New Entry to Carbocyclic Nucleosides: Oxidative Coupling Reaction of Cycloalkenylsilanes with a Nucleobase Mediated by Hypervalent Iodine Reagent
  作者：Yuichi Yoshimura、Masatoshi Ohta、Tatsushi Imahori、Tomozumi Imamichi、Hiroki Takahata

  DOI：10.1021/ol8012155

  日期：2008.8.21

  A novel method for synthesizing carbocyclic nucleosides was developed. The new synthesis includes a direct coupling reaction of cycloalkenylsilanes with a silylated nucleobase catalyzed by a hypervalent iodine reagent. By applying the method, a novel carbocyclic cytidine derivative having bis(hydroxymethyl)cyclohexene as a pseudosugar moiety, designed as a potential anti-HIV agent, was successfully

  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。