N-trimethylsilyl-p-methoxybenzylamine | 54965-03-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: N-trimethylsilyl-p-methoxybenzylamine
• 英文别名: Silanamine, N-((4-methoxyphenyl)methyl)-1,1,1-trimethyl-；1-(4-methoxyphenyl)-N-trimethylsilylmethanamine
• CAS: 54965-03-6
• 化学式: C₁₁H₁₉NOSi
• 分子量: 209.363
• InChiKey: JDAFMRWWUIPRKI-UHFFFAOYSA-N

物化性质

• 沸点：
  255.0±15.0 °C(Predicted)
• 密度：
  0.935±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.62
• 重原子数：
  14
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  21.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  N-trimethylsilyl-p-methoxybenzylamine 在 正丁基锂 、 ammonium cerium (IV) nitrate 作用下， 以 正己烷 、 水 、 甲苯 、 乙腈 为溶剂， 反应 8.0h， 生成
  参考文献：
  名称：

  A chiral ligand mediated aza-conjugate addition strategy for the enantioselective synthesis of β-amino esters that contain hydrogenolytically sensitive functionality

  摘要：

  Aza-conjugate addition of the lithium anion of N-trimethylsilyl-p-methoxybenzylamine to tert-butyl enoate acceptors, in the presence of a stoichiometric amount of enantiopure 1,2-dimethoxy-1,2-diphenylethane and excess trimethylsilyl chloride, affords tert-butyl-N-p-methoxybenzyl-beta-amino esters with excellent levels of enantiocontrol. These N-p-methoxybenzyl-beta-amino-esters may be deprotected under oxidative conditions via treatment with ceric ammonium nitrate, followed by acid hydrolysis of the resultant imine intermediates, to afford enantiopure beta-amino-esters containing hydrogenolytically sensitive functionality. (C) 2015 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2015.08.018
• 作为产物：
  描述：

  三甲基氯硅烷 、 4-甲氧基苄胺 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 2.0h， 以79%的产率得到N-trimethylsilyl-p-methoxybenzylamine
  参考文献：
  名称：

  具有可转移伯胺的高价碘 (III) 试剂：稳定烯醇化物的亲电 α-胺化的结构和反应性

  摘要：

  描述了包含可转移伯胺基团的新系列高价碘试剂。苯并氧唑酮类试剂通过操作简单的反应以高达定量的产率在克级合成。这些工作稳定的固体通过 X 射线分析进行了表征，并成功用于茚满酮基 β-酮酯的 α-胺化，产率高达 83%。机理研究表明了一种涉及亲电子胺的取代机理。

  DOI：

  10.1021/acs.orglett.1c04312

文献信息

• Alkylthionitroso and arylthionitroso compounds generated from N-trimethylsilyl-N-chlorothioalkylamine precursors
  作者：Martin R. Bryce、Antony Chesney、Julie N. Heaton、Graham N. McKelvey、Martin Anderson

  DOI：10.1016/s0040-4039(00)77083-3

  日期：1994.7

  A range of alkylthionitroso and arylthionitroso compounds have been generated by thermal fragmentation of N-trimethylsilyl-N-chlorothioalkyl(aryl)amine precursors, and intercepted by reaction with dimethylbutadiene to afford Diels-Alder and ene adducts.

  N-三甲基甲硅烷基-N-氯硫代烷基（芳基）胺前体的热裂解产生了一系列烷基硫代亚硝基和芳基硫代亚硝基化合物，并通过与二甲基丁二烯反应而截获了狄尔斯-阿尔德和烯加合物。
• Zirconium Hydroaminoalkylation. An Alternative Disconnection for the Catalytic Synthesis of α-Arylated Primary Amines
  作者：Ana Koperniku、Paul J. Foth、Glenn M. Sammis、Laurel L. Schafer

  DOI：10.1021/jacs.9b10465

  日期：2019.12.4

  Primary amine products have been prepared using zirconium catalyzed hydroaminoalkylation of alkenes with N-silylated benzylamine substrates. Catalysis using commercially available Zr(NMe2)4, affords an alternative disconnection to access α-arylated primary amines upon aqueous work-up. Substrate dependent regio- and diastereoselectivity of the reaction is observed. Bulky substituents on the terminal

  已经使用锆催化的烯烃与 N-甲硅烷基化苄胺底物的加氢氨基烷基化制备了伯胺产物。使用市售的 Zr(NMe2)4 催化，提供了另一种断开连接，以在水处理后获得 α-芳基化伯胺。观察到反应的底物依赖性区域选择性和非对映选择性。末端烯烃上的大体积取代基专门生成线性区域异构体。在三氟乙基化-α-芳基化胺的制备中，突出了这种用于合成可以进行进一步合成加工的结构单元的原子经济催化策略。
• Organosilicon synthesis of isocyanates: II. Synthesis of aliphatic, carbocyclic, and fatty-aromatic isocyanates
  作者：A. V. Lebedev、A. B. Lebedeva、V. D. Sheludyakov、S. N. Ovcharuk、E. A. Kovaleva、O. L. Ustinova

  DOI：10.1134/s1070363206030182

  日期：2006.3

  Silylation of a series of aliphatic, carbocyclic, and fatty-aromatic amines gave the corresponding silyl derivatives whose yield depended on the electronic and steric structure of the substrate and the nature of the silylating agent. The yield of isocyanates obtained by phosgenation of the silyl derivatives under mild conditions decreased in going from aliphatic amines to benzylamines and rose as the length of the alkyl chain in fatty-aromatic amines extended. The most convenient procedure for the synthesis of low-boiling alkyl isocyanates was found to be based on the transformation of amines or ammonium salts into silyl or silyl silyl-carabamates. followed by pyrolysis of the latter in the presence of trichloro(phenyl)silane.
• Reactions of Secondary Amines with Bis(η⁵:η¹-pentafulvene)titanium Complexes: Formation of Titanium Amides and Titanaaziridines
  作者：Manfred Manßen、Nicolai Lauterbach、Tim Woriescheck、Marc Schmidtmann、Rüdiger Beckhaus

  DOI：10.1021/acs.organomet.6b00915

  日期：2017.2.27

  The reactions of bis (eta(5):eta(1)-pentafulvene)titanium complexes (1) with 19 different secondary amines (Aa-s) have been investigated. Depending on the substitution pattern of 1 and nature of the amine used, different reaction products are formed. With use of bis(eta(5):eta(1)-di(p-tolyl)-pentafulvene)titanium (1b) and N-methylanilines (Aa,b), N-methylbenzylamines (Ac,d), N-methylcyclohexylamine (Ae), and dibenzylamine (Af), titanium monoamides of the type (eta(S)-C5H4CH(p-tolyl)(2))(eta(5):eta(1)-C5H4=C(p-tolyl)(2)TiNR2 (2a-f) have been isolated in high yields and characterized, including by single-crystal X-ray diffraction. By the reactions of eta(5):eta(1)-adamantylidene)titanium (1a) and Af, diethylamine (Ag), and 2-methylpiperidine (Ah) similar monoamides 3f-h are formed. The formation of titanium bis-amides employing different types of secondary amines (Aa-s) is not observed. The formation of titanaaziridines is observed exclusively by using 1a and N-methylanilines (Aa,b), N-benzylphenylamine (Ai), and N-benzyltrimethylsilylamines (Aj,k). The titanaaziridine 4i undergoes a regioselective ring enlargement reaction with 1-hexyne. By the reaction of 4i and phenylacetylene a ring opening with formation of (Cp-Ad)(2)Ti(NPh(CH2Ph)CCPh) (6) is observed. The acetylide 6 undergoes a thermal decomposition to give the zigzag butadiyne complex 7. In addition to the ring enlargement of 4j by, ketones a ketone insertion in the titanium-Cp bond is found, as proved for 8 by single-crystal X-ray diffraction.
• Bryce Martin R., Chesney Antony, Heaton Julie N., McKelvey Graham N., And+, Tetrahedron Lett, 35 (1994) N 29, S 5275- 5278
  作者：Bryce Martin R., Chesney Antony, Heaton Julie N., McKelvey Graham N., And+

  DOI：——

  日期：——