(bromo(4-methoxyphenyl)methyl)trimethylsilane | 114378-10-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: (bromo(4-methoxyphenyl)methyl)trimethylsilane
• 英文别名: [bromo-(4-methoxyphenyl)methyl]-trimethylsilane
• CAS: 114378-10-8
• 化学式: C₁₁H₁₇BrOSi
• 分子量: 273.245
• InChiKey: JIJMFQDZFFTZKO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.01
• 重原子数：
  14.0
• 可旋转键数：
  3.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  9.23
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  (bromo(4-methoxyphenyl)methyl)trimethylsilane 在 sodium nitrite 作用下， 以 甲醇 为溶剂， 生成 C₁₂H₂₀N₂O₂Si
  参考文献：
  名称：

  Novel generation of azomethine imines from α-silylnitrosamines by 1,4-silatropic shift and their cycloaddition

  摘要：

  Novel and facile generation of azomethine imines from alpha-silylnitrosamines and subsequent cycloaddition with dipolarophiles leading to a variety of pyrazole derivatives have been developed. The key to the reaction is a 1,4-silatropic shift caused by strong affinity of the nitroso oxygen atom toward the silicon atom. Thus, alpha-silylnitrosamines are treated with 1 equiv. of dipolarophiles in refluxing toluene for 1 h to give pyrazole derivatives in good to excellent yields. (C) 1999 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(99)01859-6
• 作为产物：
  描述：

  (4-甲氧基苄基)-三甲基硅烷 在 N-溴代丁二酰亚胺(NBS) 作用下， 以 四氯化碳 为溶剂， 生成 (bromo(4-methoxyphenyl)methyl)trimethylsilane
  参考文献：
  名称：

  Novel generation of azomethine imines from α-silylnitrosamines by 1,4-silatropic shift and their cycloaddition

  摘要：

  Novel and facile generation of azomethine imines from alpha-silylnitrosamines and subsequent cycloaddition with dipolarophiles leading to a variety of pyrazole derivatives have been developed. The key to the reaction is a 1,4-silatropic shift caused by strong affinity of the nitroso oxygen atom toward the silicon atom. Thus, alpha-silylnitrosamines are treated with 1 equiv. of dipolarophiles in refluxing toluene for 1 h to give pyrazole derivatives in good to excellent yields. (C) 1999 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(99)01859-6

文献信息

• Side-Chain oxidation of benzyltrimethylsilanes by iodosylbenzene in the presence of iron and manganese porphyrins
  作者：Enrico Baciocchi、Osvaldo Lanzalunga

  DOI：10.1016/s0040-4020(01)87204-5

  日期：1993.8

  presence of either iron(III) or manganese(III) tetrakis(pentafluorophenyl)porphyrin (TFPPM, with M = Fe, Mn) to give α-hydroxybenzyltrimethylsilanes, which are then rapidly converted into the corresponding benzaldehydes in the reaction medium. In these reactions the active species is the metal-oxo complex, TFPPM(V)=O, formed by iodosylbenzene and TFPPM. A relative reactivity study for a series of ring

  在铁（III）或锰（III）四（五氟苯基）卟啉（TFPPM，M = Fe，Mn）的存在下，苄基三甲基硅烷与碘基苯反应生成α-羟基苄基三甲基硅烷，然后将其快速转化为相应的苯甲醛。反应介质。在这些反应中，活性物质是由碘基苯和TFPPM形成的金属-氧配合物TFPPM（V）= O。对一系列环取代的苄基三甲基硅烷的相对反应性研究表明，当M = Fe时，该反应具有很高的选择性（ρ= -1.85），而m -MeO取代基的反应性比预期的高得多。当M = Mn时，观察到较低的ρ值（-1.15），并且在m处未发现反常反应性-MeO组。这些结果表明，通过众所周知的氢原子转移机理发生了TPFPPMn（V）＝ O引起的苄基三甲基硅烷的侧链羟基化。对于由TFPPFe（V）= O引起的相应反应，似乎更可能存在质子/电子转移耦合机制，其中可能涉及电荷转移络合物的形成。
• Development of Novel <scp>Phosphino‐Oxazoline</scp> Ligands and Their Application in Asymmetric Alkynlylation of Benzylic Halides
  作者：Rui Guo、Jiale Sang、Haijing Xiao、Junxia Li、Guozhu Zhang

  DOI：10.1002/cjoc.202200074

  日期：2022.6

  ligands derived from simple L-amino acids and 2-(diphenylphosphaneyl)benzoic acid were developed. Those mono anionic tridentated N,N,P-ligands promote the Cu-catalyzed enantioselective radical coupling of terminal alkynes with a broad range of benzylic halides including benzo-fused cyclic α-halides and α-silyl benzyl halides in high yield and excellent enantioselectivity under mild reaction conditions

  开发了一组新的立体化学多样化的膦基-恶唑啉配体，衍生自简单的L-氨基酸和 2-(二苯基膦基)苯甲酸。这些单阴离子三齿 N,N,P-配体以高产率和优异的对映选择性促进末端炔烃与多种苄基卤化物（包括苯并稠合环状 α-卤化物和 α-甲硅烷基苄基卤化物）的对映选择性自由基偶联。反应条件温和。具有多个不同的结构修饰位点，可以轻松访问各种手性 N、N、P 配体库，从而可以快速优化特定底物的配体结构。值得注意的是，苯并环分子中苄基卤键的对映选择性炔基化也是首次实现。
• Chloranil-Sensitized Photolysis of Benzyltrimethylsilanes. Solvent Effect on the Competition between Carbon-Hydrogen and Carbon-Silicon Bond Cleavage
  作者：Enrico Baciocchi、Tiziana Del Giacco、Fausto Elisei、Marcella Ioele

  DOI：10.1021/jo00129a044

  日期：1995.12

  A steady state and laser flash photolysis study of the chloranil (CA)-sensitized oxidation of benzyltrimethylsilane (BTS) and (4-methoxybenzyl)trimethylsilane (MBTS) in different solvents (benzene, CH2Cl2, and MeCN) has been carried out. In benzene, BTS reacts with (3)CA* to give exclusively alpha-substituted benzyltrimethylsilane, whereas with MBTS the alpha-substituted silane is formed together with benzylic desilylation products. The latter situation also holds in CH2Cl2 for BTS. Only desilylation products are obtained from MBTS in CH2Cl2 and from both BTS and MBTS in MeCN. Higher quantum yields in the reactions with BTS than in those with MBTS have been observed in benzene and CH2Cl2. In MeCN, no significant change in quantum yield has been observed on going from BTS to MBTS. In MeCN with both BTS and MBTS and in CH2Cl2 with MBTS, the laser photolysis experiments have shown evidence for the formation of transients which can be attributed to MBTS(.+) and CA(.-) (MBTS in MeCN and CH2Cl2) and to CA(.-) (BTS in MeCN). This indicates that quenching of (3)CA* has taken place via an electron transfer process. Once formed, both BTS.+ and MBTS(.+) undergo exclusive C-Si bond cleavage. In CH2Cl2, this reaction is promoted by CA(.-), and accordingly, MBTS(.+) decays by a second-order kinetics. In MeCN, MBTS(.+) decays by a first-order kinetics and desilylation is promoted by the solvent itself. The same holds for BTS.+ as the decay reaction of this cation radical in MeCN appears much faster than that of CA(.-). In fact, only the transient assigned to the latter species has been observed in the laser photolysis experiments. A different situation has been found for both MBTS and BTS in benzene and BTS in CH2Cl2, where quenching of (3)CA* occurs via a partial charge transfer (CT) triplet complex. The reversible formation of this complex with MBTS in benzene is clearly indicated by the dependence of the observed rate constant for 3CA* quenching on the substrate concentration, which has allowed the association constant for the complex(ca. 400 M(-1)) to be determined. With BTS in benzene and CH2Cl2, the formation of the CT triplet complex is irreversible and rate determining, and the main evidence in this respect comes from the absence of a sizable deuterium kinetic isotope effect for the 3CA* quenching rate. With BTS in benzene, the CT complex undergoes C-H bond cleavage as the exclusive chemical reaction. With MBTS in benzene and BTS in CH2Cl2, both C-H and C-Si bond cleavages take place, and it is suggested that the cleavage of the latter bond requires more transfer of charge in the complex than the cleavage of the C-H bond. Alternatively, in CH2Cl2, the CT complex might evolve in part to a solvent-separated radical ion pair, exclusively leading to the C-Si bond cleavage products. The above results have also allowed an assessment of the scope of the benzyltrimethylsilane probe to detect electron transfer mechanisms.