1-benzyl-1-methylsilacyclobutane | 3944-07-8

• 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-benzyl-1-methylsilacyclobutane
• 英文别名: 1-benzyl-1-methyl-siletane；1-Benzyl-1-methyl-monosilacylobutene；1-Methyl-1-benzyl-1-silacyclobutan；1-Benzyl-1-methyl-silacyclobutan；1-Phenyl-1-methyl-silacyclobutan；1-Benzyl-1-methyl-1-silacyclobutane；1-benzyl-1-methylsiletane
• CAS: 3944-07-8
• 化学式: C₁₁H₁₆Si
• 分子量: 176.334
• InChiKey: CPANRGXFLWTXBT-UHFFFAOYSA-N

物化性质

• 沸点：
  73.5-74 °C(Press: 5 Torr)
• 密度：
  0.94 g/cm3

计算性质

• 辛醇/水分配系数(LogP)：
  3.25
• 重原子数：
  12
• 可旋转键数：
  2
• 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-benzyl-1-methylsilacyclobutane 以 正己烷 为溶剂， 生成 1-methylene-6-(1-methylsilacyclobutyl)-2,4-cyclohexadiene
  参考文献：
  名称：

  The one- and two-photon photochemistry of benzylsilacyclobutanes, acyclic benzylsilanes, and 1,1,2-triphenylsilacyclobutane

  摘要：

  已完成。

  DOI：

  10.1139/v99-249
• 作为产物：
  描述：

  溴甲苯 、 1-氯-1-甲基硅杂环丁烷 在 magnesium 作用下， 以 乙醚 为溶剂， 反应 48.0h， 以29%的产率得到1-benzyl-1-methylsilacyclobutane
  参考文献：
  名称：

  The one- and two-photon photochemistry of benzylsilacyclobutanes, acyclic benzylsilanes, and 1,1,2-triphenylsilacyclobutane

  摘要：

  已完成。

  DOI：

  10.1139/v99-249

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 to 8‐Membered Silacycles through Formal Cross‐Dimerization of 5‐Membered Palladacycles with Silacyclobutanes
  作者：Xi–Chao Wang、Hao‐Ran Wang、Xiufang Xu、Dongbing Zhao

  DOI：10.1002/ejoc.202100535

  日期：2021.6.7

  Described herein, the chemo- and regio-selective ring expansion of silacyclobutanes to sila-8-membered ring fused biaryl skeletons, enabled by Pd-catalytic conditions. This strategy involves C−C bond cleavage or C(sp2/sp3)−H bond activation and C−Si bond cleavage followed by a double reductive elimination process. DFT calculations indicate that the C−H bond activation or C−C bond cleavage to form palladacycle

  在本文中描述了通过 Pd 催化条件实现的硅环丁烷的化学和区域选择性扩环到 sila-8 元环稠合联芳基骨架。该策略涉及 C-C 键断裂或 C( sp 2 / sp 3 )-H 键活化和 C-Si 键断裂，然后是双还原消除过程。DFT 计算表明，C-H 键活化或 C-C 键断裂形成钯环物种在开始时比硅杂环丁烷的 C-Si 键断裂在能量上更有利。
• 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。
• The one- and two-photon photochemistry of benzylsilacyclobutanes, acyclic benzylsilanes, and 1,1,2-triphenylsilacyclobutane
  作者：William J Leigh、Thomas R Owens

  DOI：10.1139/v99-249

  日期：2000.11.1

  The photochemistry of several α-silylbenzyl compounds has been investigated in hexane and in methanol solution. Direct photolysis of 1-benzyl-1-methylsilacyclobutane (1) in methanolic hexane solution produces 1-propyl-1-methyl-2,3-benzosilacyclobutene (6) in quantitative yield, by a sequential two-photon process involving the photoactive isotoluene derivative 1-methylene-6-(1-methylsilacyclobutyl)-2,4-cyclohexadiene (13a), which has been identified on the basis of its ¹H NMR and UV absorption spectra. In contrast, direct irradiation of 1-benzyl-1-phenylsilacyclobutane (2) under similar conditions results in the formation of a complex mixture of products consistent with the competing formation of 1-benzyl-1-phenylsilene and benzyl- and 1-phenylsilacyclobutyl radicals. The silene is a transient which has been detected directly by laser flash photolysis of 2 (λ_max = 315 nm, τ ~ 4.5 µs). Free radical formation is shown to be due to secondary photolysis of a second primary product, 1-methylene-6-(1-phenylsilacyclobutyl)-2,4-cyclohexadiene (13b), which has also been detected and identified by static UV absorption (λ_max = 335 nm) and ¹H NMR spectroscopy. In a reaction with some analogy to the acid-catalyzed desilylation of allylsilanes, both 13a and 13b can be intercepted in neutral or acidic methanol solution to yield toluene and 1-methyl- or 1-phenyl-1-methoxysilacyclobutane, respectively. Direct photolysis of benzyldimethylphenylsilane (4) also leads to the formation of the corresponding isotoluene derivative, while benzyltrimethylsilane (3) exhibits negligible photoreactivity. The endocyclic benzylsilane 1,1,2-triphenylsilacyclobutane (5) is shown to undergo competing [2 + 2]-cycloreversion and [1,3]-silyl migration to yield a bicyclic isotoluene analogue, which reacts rapidly with methanol to yield the acyclic methoxysilane reported previously to be the main product of photolysis of this silacyclobutane in methanol solution. Relative quantum yields for isotoluene formation from photolysis of 1-4 and absolute rate constants for methanolysis of several of these compounds under neutral and acidic conditions have also been determined.Key words: photochemistry, organosilicon, benzylsilane, silacyclobutane, silene, kinetics, isotoluene.

  已完成。