1-methyl-1-(2-methylphenyl)silacyclobutane | 630402-83-4

• 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: 1-methyl-1-(2-methylphenyl)silacyclobutane
• 英文别名: 1-methyl-1-(o-tolyl)siletane；1-Methyl-1-(o-methylphenyl)-1-silacyclobutane；1-methyl-1-(2-methylphenyl)siletane
• CAS: 630402-83-4
• 化学式: C₁₁H₁₆Si
• 分子量: 176.334
• InChiKey: DFOADNKIMSILPG-UHFFFAOYSA-N

物化性质

• 沸点：
  220.7±19.0 °C(Predicted)
• 密度：
  0.93±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.68
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.45
• 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：

  1-methyl-1-(2-methylphenyl)silacyclobutane 在 potassium fluoride 、 双氧水 、 potassium hydrogencarbonate 作用下， 以 四氢呋喃 、 甲醇 、 水 为溶剂， 反应 6.0h， 以74%的产率得到邻甲酚
  参考文献：
  名称：

  Oxidation of Carbon−Silicon Bonds:  The Dramatic Advantage of Strained Siletanes

  摘要：

  Herein we report on the use of siletanes as substrates for the oxidation of carbon-silicon bonds. These tetraalkylsilanes are easy to handle yet susceptible to rapid ring opening and oxidation upon exposure to aqueous fluoride and peroxide. This combination of stability and reactivity presents many practical benefits, including compatibility with silicon protecting groups and electron-rich aromatic rings.

  DOI：

  10.1021/ol035695y
• 作为产物：
  描述：

  邻甲苯基溴化镁 以 四氢呋喃 、 乙醚 为溶剂， 反应 71.0h， 生成 1-methyl-1-(2-methylphenyl)silacyclobutane
  参考文献：
  名称：

  Palladium-Catalyzed Desymmetrization of Silacyclobutanes with Alkynes: Enantioselective Synthesis of Silicon-Stereogenic 1-Sila-2-cyclohexenes and Mechanistic Considerations

  摘要：

  A palladium-catalyzed enantioselective desymmetrization of silacyclobutanes with alkynes has been developed to give silicon-stereogenic 1-sila-2-cyclohexenes with high enantioselectivity. The products thus obtained undergo further derivatizations with complete stereoselectivity, and a new catalytic cycle involving alkyne coordination (oxidative cyclization)-transmetalation (sigma-bond metathesis)-reductive elimination has also been proposed.

  DOI：

  10.1021/ol301191u

文献信息

• Rhodium‐Catalyzed Reaction of Silacyclobutanes with Unactivated Alkynes to Afford Silacyclohexenes
  作者：Hua Chen、Yi Chen、Xiaoxiao Tang、Shunfa Liu、Runping Wang、Tianbao Hu、Lu Gao、Zhenlei Song

  DOI：10.1002/anie.201814143

  日期：2019.3.26

  A Rh‐catalyzed reaction of silacyclobutanes (SCBs) with unactivated alkynes has been developed to form silacyclohexenes with high chemoselectivity. Good enantioselectivity at the stereogenic silicon center was achieved using a chiral phosphoramidite ligand. The resulting silacyclohexenes are useful scaffolds for synthesizing structurally attractive silacyclic compounds.

  硅烷环丁烷（SCB）与未活化炔烃的Rh催化反应已被开发出来，可形成具有高化学选择性的硅烷环己烯。使用手性亚磷酰胺配体在立体硅中心具有良好的对映选择性。所得的硅杂环己烯是用于合成结构上有吸引力的硅环化合物的有用的支架。
• Ring Expansion of Silacyclobutanes with Allenoates to Selectively Construct 2- or 3-(<i>E</i>)-Enoate-Substituted Silacyclohexenes
  作者：Xiaoxiao Tang、Yan Zhang、Yulang Tang、Yi Li、Jiajing Zhou、Duyang Wang、Lu Gao、Zhishan Su、Zhenlei Song

  DOI：10.1021/acscatal.1c05831

  日期：2022.5.6

  structural diversity of silacycles has been largely limited due to the lack of general synthetic methods. Here, we report an efficient synthesis of exo-cyclic enoate-substituted silacyclohexenes by the ring expansion of silacyclobutanes with allenoates. The reaction proceeds with two regioselectivities during Si–C bond insertion. In the presence of the Pd/PR3 catalyst, unsubstituted allenoates undergo β, γ-insertion

  硅环是含硅功能分子中最重要的核心框架之一。然而，由于缺乏通用的合成方法，硅环的结构多样性在很大程度上受到了限制。在这里，我们报告了通过硅环丁烷与烯丙酸酯的扩环来有效合成外环烯酸酯取代的硅环己烯。在 Si-C 键插入过程中，反应以两种区域选择性进行。在 Pd/PR 3催化剂存在下，未取代的烯丙酸酯经历 β, γ-插入形成 Si-Cβ 键，得到 2-( E)-烯酸酯取代的硅环己烯。在该途径中，手性亚磷酰胺配体用于对映选择性构建立体硅中心。在第二种途径中，在 PtCl 2催化剂存在下，α-取代的烯丙酸酯经历 γ，β-插入形成 Si-Cγ 键，产生 3-( E )-烯酸酯取代的硅环己烯。已经进行了控制实验和密度泛函理论计算，以了解 Pd 和 Pt 催化的扩环反应的区域和立体化学结果。
• Rhodium-Catalyzed Hydrolytic Cleavage of the Silicon–Carbon Bond of Silacyclobutanes to Access Silanols
  作者：Wei-Ke Zhu、Hua-Jie Zhu、Xiao-Jun Fang、Fei Ye、Jian Cao、Zheng Xu、Li-Wen Xu

  DOI：10.1021/acs.orglett.3c02611

  日期：2023.10.6

  Herein, we report the first rhodium-catalyzed hydrolytic cleavage of the silicon–carbon bond in silacyclobutanes using water as the reactant. A series of silacyclobutanes could be employed in this reaction in the presence of the Rh/BINAP complex, resulting in the corresponding silanols in good yields. Additionally, a chiral 1,1,4,4-tetraaryl-2,3-O-isopropylidene-l-threitol-derived phosphoramidite ligand

  在此，我们报告了首次以水为反应物，铑催化硅杂环丁烷中硅碳键的水解断裂。在 Rh/BINAP 络合物存在下，可以在该反应中使用一系列硅杂环丁烷，从而以良好的产率产生相应的硅烷醇。此外，手性1,1,4,4-四芳基-2,3- O-异亚丙基-1-苏糖醇衍生的亚磷酰胺配体可用于该反应，以产生具有良好对映选择性的Si-立体硅烷醇。
• Oxidation of Carbon−Silicon Bonds:  The Dramatic Advantage of Strained Siletanes
  作者：James D. Sunderhaus、Hubert Lam、Gregory B. Dudley

  DOI：10.1021/ol035695y

  日期：2003.11.1

  Herein we report on the use of siletanes as substrates for the oxidation of carbon-silicon bonds. These tetraalkylsilanes are easy to handle yet susceptible to rapid ring opening and oxidation upon exposure to aqueous fluoride and peroxide. This combination of stability and reactivity presents many practical benefits, including compatibility with silicon protecting groups and electron-rich aromatic rings.
• Palladium-Catalyzed Desymmetrization of Silacyclobutanes with Alkynes: Enantioselective Synthesis of Silicon-Stereogenic 1-Sila-2-cyclohexenes and Mechanistic Considerations
  作者：Ryo Shintani、Kohei Moriya、Tamio Hayashi

  DOI：10.1021/ol301191u

  日期：2012.6.1

  A palladium-catalyzed enantioselective desymmetrization of silacyclobutanes with alkynes has been developed to give silicon-stereogenic 1-sila-2-cyclohexenes with high enantioselectivity. The products thus obtained undergo further derivatizations with complete stereoselectivity, and a new catalytic cycle involving alkyne coordination (oxidative cyclization)-transmetalation (sigma-bond metathesis)-reductive elimination has also been proposed.