[2-(4-chlorophenyl)allyl]trimethylsilane | 1421842-53-6

• 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: [2-(4-chlorophenyl)allyl]trimethylsilane
• 英文别名: 2-(4-Chlorophenyl)prop-2-enyl-trimethylsilane
• CAS: 1421842-53-6
• 化学式: C₁₂H₁₇ClSi
• 分子量: 224.805
• InChiKey: KGZKGELAMDVARC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.69
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 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：

  [2-(4-chlorophenyl)allyl]trimethylsilane 、 苯甲酰基(苯基碘代)(三氟甲磺酰基)甲烷化物 在 copper (II)-fluoride 作用下， 以 N,N-二甲基乙酰胺 为溶剂， 反应 10.0h， 以81%的产率得到(2-(4-chlorophenyl)allyl)(trifluoromethyl)sulfane
  参考文献：
  名称：

  铜催化下三氟甲磺酰基超高价碘鎓叶立德对烯丙基硅烷和甲硅烷基烯醇醚的三氟甲基硫醇化反应

  摘要：

  已经进行了烯丙基硅烷和甲硅烷基烯醇醚与三氟甲磺酰基高价碘鎓叶立德的亲电子三氟甲基硫醇化反应。在催化量的CuF 2的存在下，反应在温和的条件下以中等至高收率进行。

  DOI：

  10.1021/acs.orglett.5b00057
• 作为产物：
  描述：

  对氯苯酚 在 吡啶 、 1,1'-双(二苯基膦)二茂铁 、 palladium diacetate 、 三乙胺 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 22.0h， 生成 [2-(4-chlorophenyl)allyl]trimethylsilane
  参考文献：
  名称：

  Stereoselective Entry into α,α’‐C‐Oxepane Scaffolds through a Chalcogen Bonding Catalyzed Strain‐Release C‐Septanosylation Strategy

  摘要：

  The utility of unconventional noncovalent interactions (NCIs) such as chalcogen bonding has lately emerged as a robust platform to access synthetically difficult glycosides stereoselectively. Herein, we disclose the versatility of a phosphonochalcogenide (PCH) catalyst to facilitate access into the challenging, but biologically interesting 7‐membered ring α,α’‐C‐disubstituted oxepane core through an α‐selective strain‐release C‐glycosylation. Methodically, this strategy represents a switch from more common but entropically less desired macrocyclizations to a thermodynamically favored ring‐expansion approach. In light of the general lack of stereoselective methods to access C‐septanosides, a remarkable palette of silyl‐based nucleophiles can be reliably employed in our method. This include a broad variety of useful synthons, such as easily available silyl‐allyl, silyl‐enol ether, silyl‐ketene acetal, vinylogous silyl‐ketene acetal, silyl‐alkyne and silylazide reagents. Mechanistic investigations suggest that a mechanistic shift towards an intramolecular aglycone transposition involving a pentacoordinate silicon intermediate is likely responsible in steering the stereoselectivity.

  DOI：

  10.1002/anie.202405706

文献信息

• Selective C–F Bond Allylation of Trifluoromethylalkenes
  作者：Chuan Zhu、Meng‐Meng Sun、Kai Chen、Haidong Liu、Chao Feng

  DOI：10.1002/anie.202106531

  日期：2021.9.6

  trifluoromethylalkene derivatives. By using readily available allyl metallics as nucleophilic coupling partner, the present reaction enables an expedient construction of structurally diversified CF2-bridged 1,5-dienes. Furthermore, the exquisite selectivity observed in this transformation is revealed to be based on the underlying mechanism that consists of a cascade of nucleophilic SN2′ defluorinative

  CF 3基团的选择性 C-F 键官能化代表了一种吸引药学特权的二氟亚甲基部分的结合策略。尽管最近在 Ar-CF 3分子的官能化方面取得了重大进展，但适用于烯基-CF 3同类物的处方仍然不够充分。在此，我们报告了三氟甲基烯烃衍生物的 C-F 键制备的战略性新颖方案。通过使用容易获得的烯丙基金属作为亲核偶联伙伴，本反应能够方便地构建结构多样化的 CF 2-桥接的 1,5-二烯。此外，在该变换中观察到的精美选择性显露是基于其由亲核S的级联的基本机制Ñ 2'defluorinative烯丙基化并以电子方式促进Cope重排。
• Silver-promoted cross-coupling of substituted allyl(trimethyl)silanes with aryl iodides by palladium catalysis
  作者：Zhen-Lin Hou、Fan Yang、Zhibing Zhou、Yu-Fei Ao、Bo Yao

  DOI：10.1016/j.tetlet.2018.11.026

  日期：2018.12

  A ligand-free Pd-catalyzed cross-coupling of substituted allyl(trimethyl)silanes with aryl iodides enabled by silver salts was developed. This reaction delivered allylic arenes chemoselectively and regioselectively. The study suggested that the reaction might proceed through oxidative addition of ArI to Pd(0) followed by halide abstraction to give an electrophilic complex ArPdX, which further reacted

  开发了无配位体的钯催化的取代的烯丙基（三甲基）硅烷与由银盐形成的芳基碘化物的交叉偶联。该反应通过化学选择性和区域选择性递送烯丙基芳烃。研究表明该反应可能通过将ArI氧化加成到Pd（0）上，然后进行卤化物的抽提而得到亲电配合物ArPdX，后者通过亲电加成/去甲硅烷基化/还原消除反应与烯丙基三甲基硅烷进一步反应得到烯丙基芳基偶联剂产品。
• Oxidative cross-coupling of allyl(trimethyl)silanes with aryl boronic acids by palladium catalysis
  作者：Zhibing Zhou、Zhen-Lin Hou、Fan Yang、Bo Yao

  DOI：10.1016/j.tet.2018.10.055

  日期：2018.12

  allylsilanes with aryl boronic acids has been developed by palladium catalysis. The reaction between β-substituted allyl(trimethyl)silanes and a wide range of aryl boronic acids afforded allylarenes in moderate to good yields and excellent selectivity. On the basis of experimental results and literature reports, it was suggested that the reaction might start from transmetalation of aryl boronic acid with AgOAc

  烯丙基硅烷与芳基硼酸的第一次氧化交叉偶联已通过钯催化发展。β-取代的烯丙基（三甲基）硅烷与各种芳基硼酸之间的反应以中等至良好的产率和优异的选择性提供了烯丙基芳烃。根据实验结果和文献报道，有人认为该反应可能始于芳基硼酸与AgOAc的重金属化反应，然后与Pd（II）的重金属化反应，从而制得乙酸芳基钯配合物作为关键中间体。将该中间体与烯丙基硅烷进行亲电加成/去甲硅烷基化或金属转移，然后还原消除，得到最终产物。
• Palladium-catalyzed direct C H allylation of indoles derivatives with allyltrimethylsilanes
  作者：Lun Wang、Yuanhao He、Zhi Li、linchun Zhang、Baoming Fan、Fen Zhao、Minghong Chen

  DOI：10.1016/j.tetlet.2023.154689

  日期：2023.10

  palladium-catalyzed cross-coupling reaction between 2-susbtituted indole and allyltrimethylsilanes in the absence of fluoride anion source was studied. The optimal conditions for the reaction were identified after various reaction conditions examined, using Pd(OAc)2 as the catalyst, Cu(OTf)2 as oxidant, and DMSO as solvent, leading to the synthesis of a series of benzindoles bearing allyl group in good to high yields

  研究了在没有氟化物阴离子源的情况下钯催化的 2-取代吲哚和烯丙基三甲基硅烷之间的交叉偶联反应。通过考察各种反应条件，确定了最佳反应条件，以Pd(OAc) 2为催化剂，Cu(OTf) 2为氧化剂，DMSO为溶剂，合成了一系列带有烯丙基的苯并吲哚。产量从好到高。
• The γ-silicon effect. III.1 The Yukawa-Tsuno treatment in the solvolysis of 2-aryl-3-(trimethylsilyl)propyl tosylates
  作者：Tohru Nakashima、Ryoji Fujiyama、Mizue Fujio、Yuho Tsuno

  DOI：10.1016/s0040-4039(98)02434-4

  日期：1999.1

  Solvolysis of 2-aryl-3-(trimethylsilyl)propyl tosylate revealed the competitive assistances of the β-aryl and β-(trimethylsilyl)methyl groups. It is found out that the enhanced reactivity by the percaudal interaction of trimethylsilylmethyl group is comparable with that by π-participation of β-phenyl group, and is extraordinarily larger than that by σ-participation of the alkyl group.

  2-芳基-3-（三甲基甲硅烷基）丙基甲苯磺酸盐的溶剂分解显示了β-芳基和β-（三甲基甲硅烷基）甲基的竞争性辅助。发现通过三甲基甲硅烷基甲基的尾端相互作用增强的反应性与通过β-苯基的π-参与的增强的反应性相当，并且比通过烷基的σ-参与的增强的反应性大。