(4-羟基苄基)三甲基硅烷 | 17993-96-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: (4-羟基苄基)三甲基硅烷
• 英文名称: p-<(Trimethylsilyl)methyl>benzyl alcohol
• 英文别名: (4-((trimethylsilyl)methyl)phenyl)methanol；4-[(trimethylsilyl)methyl]benzyl alcohol；4-(trimethylsilylmethyl)benzyl alcohol；Trimethylsilyl-benzyl-4-hydroxymethyl；[4-(Trimethylsilylmethyl)phenyl]methanol
• CAS: 17993-96-3
• 化学式: C₁₁H₁₈OSi
• 分子量: 194.349
• InChiKey: YUZORMOVKGRVSU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (4-羟基苄基)三甲基硅烷 在 盐酸 、 magnesium 作用下， 反应 18.0h， 生成 methyl 2-[4-[(1,4-dicyano-2H-naphthalen-1-yl)methyl]phenyl]acetate
  参考文献：
  名称：

  Methylbenzene cation radical .alpha.-fragmentation selectivities revealed in SET-photoadditions of p-xylene derivatives to 1,4-dicyanonaphthalene [SET = single electron transfer]

  摘要：

  SET-promoted photoreactions of selected p-xylene derivatives, including p-xylene (3a), p-phenylenediacetic acid (3b), p-bis[(trimethylsilyl)methyl]benzene (3c), p-[(trim ethylsilyl)methyl]toluene (3d), p-tolylacetic acid (3e), and p-[(trimethylsilyl)methyl]phenylacetic acid (3f), to 1,4-dicyanonaphthalene have been investigated. These processes lead to clean and selective formation of 1:1 adducts whose nature is controlled by alpha-heterolytic fragmentation reactions occurring at benzylic positions of arene cation radicals which serve as key reactive intermediates. The results indicate that the relative rates of cation radical fragmentations of the type ([ArCH2E].+ + B: --> ArCH2.+ BE) depend on the nature of the electrofugal group, E, in the following order: E = SiMe3 > CO2H > H. The experimental basis for these conclusions is discussed.

  DOI：

  10.1021/jo00056a029
• 作为产物：
  描述：

  4-((三甲基甲硅烷基)甲基)苯甲酸 在 lithium aluminium tetrahydride 作用下， 以 乙醚 为溶剂， 反应 0.25h， 以94%的产率得到(4-羟基苄基)三甲基硅烷
  参考文献：
  名称：

  Room Temperature Observation of p-Xylylenes by ¹H NMR and Evidence for Diradical Intermediates in Their Oligomerization

  摘要：

  p-Quinodimethanes (p-QDMs) are reactive molecules that have been invoked as transient intermediates in a number of reactions. Dilute solutions of benzene-based p-QDMs, p-xylylene (1), a-methyl-p-xylylene (10), and 2,5-dimethyl-p-xylylene (11) can be prepared by fluoride-induced elimination of trimethylsilyl acetate from the appropriate precursor. It has been found that these solutions are stable enough to allow these reactive p-QDMs to be observed by H-1 NMR spectroscopy at room temperature. For the first time, the 13 C NMR spectrum of p-QDM 1 was observed. After several hours at room temperature, these p-QDMs form dimers, trimers, and insoluble oligomers. Formation of trimers provides evidence that p-QDMs 1, 10, and 11 dimerize by a stepwise mechanism involving dimeric diradicals as intermediates.

  DOI：

  10.1021/jo0516279

文献信息

• The trimethylsilyl xylyl (TIX) ether: a useful protecting group for alcohols
  作者：Ch. Raji Reddy、Amar G. Chittiboyina、Rajashaker Kache、Jae-Chul Jung、E. Blake Watkins、Mitchell A. Avery

  DOI：10.1016/j.tet.2004.11.023

  日期：2005.1

  A new protecting group for alcohols, the p-trimethylsilyl xylyl (TIX) group has been developed. The TIX group is used to protect various alcohols under acidic as well as basic conditions. The protected ethers thus formed had noteworthy chemoselectivity upon deprotection in the presence of other benzyl ethers and commonly used protecting groups. The stability of the TIX group towards various reagents

  已开发出一种新的醇保护基，对-三甲基甲硅烷基二甲苯基（TIX）。TIX基团用于在酸性和碱性条件下保护各种醇。这样形成的被保护的醚在其他苄基醚和常用保护基的存在下脱保护后具有显着的化学选择性。还检查了TIX基团对各种试剂的稳定性。
• [EN] NOVEL PROTECTING REAGENTS, PROTECTING GROUPS AND METHODS OF FORMING AND USING THE SAME<br/>[FR] NOUVEAUX REACTIFS DE PROTECTION, GROUPES DE PROTECTION, ET METHODES DE FORMATION ET D'UTILISATION DESDITS REACTIFS ET GROUPES
  申请人：UNIV MISSISSIPI

  公开号：WO2005100329A1

  公开（公告）日：2005-10-27

  New protecting reagents are provided that allow for the selective placement of a new protecting group onto a reactive site of a multifunctional compound. The reagents are 2, 3, and 4-trialkylsilylxylyl, triarylsilylxylyl or a combination of alkyl-aryl silylxylyl reagents (TIX reagents), which carry a TIX protecting group for protecting alcohols as ethers, urethanes, carbonates, acetals; amines as carbamates or ureas; and thiols as ethers or esters. The invention also provides methods of forming the 2, 3, and 4-TIX reagents; introducing the TIX protecting groups to molecules bearing hydroxyl groups, amine groups, or thiol groups; methods of removing the TIX protecting groups; and intermediate compounds formed during any one of these methods. The invention further provides methods useful in producing epothilones and analogs and derivatives thereof.

  提供了一种新的保护试剂，它允许将一个新的保护基团选择性地放置在多功能化合物的反应位点上。这些试剂是2、3和4-三烷基硅氧基苄基，三芳基硅氧基苄基或烷基-芳基硅氧基苄基试剂（TIX试剂）的组合，它们带有TIX保护基团，用于将醇作为醚、尿烷、碳酸酯、缩醛进行保护；将胺作为碳酸酰胺或尿素进行保护；以及将硫醇作为醚或酯进行保护。本发明还提供了形成2、3和4-TIX试剂的方法；将TIX保护基团引入带有羟基、胺基或巯基的分子中的方法；移除TIX保护基团的方法；以及在这些方法中的任一步骤形成的中间化合物。本发明进一步提供了用于生产epothilones及其类似物和衍生物的有用方法。
• Metal-Catalyzed Dealkoxylative C_arylC sp 3 Cross-Coupling-Replacement of Aromatic Methoxy Groups of Aryl Ethers by Employing a Functionalized Nucleophile
  作者：Matthias Leiendecker、Chien-Chi Hsiao、Lin Guo、Nurtalya Alandini、Magnus Rueping

  DOI：10.1002/anie.201402922

  日期：2014.11.17

  The direct replacement of aromatic methoxy groups with activated carbon nucleophiles would give rise to novel synthetic pathways for targeted and diversity‐oriented syntheses. We demonstrate here that this transformation can be achieved in a one‐step reaction involving a bifunctional organolithium nucleophile in combination with a CArOMe bond‐cleaving nickel catalyst. The resulting products are stable

  用活性炭亲核试剂直接取代芳族甲氧基将为靶向和面向多样性的合成提供新颖的合成途径。我们在这里表明，这种转化可以在涉及组合的双官能有机锂的亲核试剂与C的一步反应来实现的Ar  OME键的裂解镍催化剂。生成的产物稳定，具有α-CH活性，并适用于各种进一步的修饰。
• Nickel-Catalyzed Csp²–Csp³Bond Formation via C–F Bond Activation
  作者：Yee Ann Ho、Matthias Leiendecker、Xiangqian Liu、Chengming Wang、Nurtalya Alandini、Magnus Rueping

  DOI：10.1021/acs.orglett.8b02351

  日期：2018.9.21

  A nickel-catalyzed cross coupling of aryl fluorides via C–F bond activation has been developed. The alkylation method allows selective replacement of aryl fluorides by alkyl groups and enables the synthesis of diverse and otherwise difficult to access scaffolds in good yields.

  已经开发了一种通过C-F键活化的镍催化的芳基氟化物交叉偶联。烷基化方法允许烷基选择性取代芳基氟化物，并能够以高收率合成多种多样的且难以获得的支架。
• Palladium-Catalyzed C(<i>sp</i>³)–C(<i>sp</i>²) Cross-Coupling of (Trimethylsilyl)methyllithium with (Hetero)Aryl Halides
  作者：Dorus Heijnen、Valentín Hornillos、Brian P. Corbet、Massimo Giannerini、Ben L. Feringa

  DOI：10.1021/acs.orglett.5b00905

  日期：2015.5.1

  The palladium-catalyzed direct cross-coupling of a range of organic chlorides and bromides with the bifunctional C(sp3)-(trimethylsilyl)methyllithium reagent is reported. The use of Pd-PEPPSI-IPent as the catalyst allows for the preparation of structurally diverse and synthetically versatile benzyl- and allylsilanes in high yields under mild conditions (room temperature) with short reaction times.

  报道了钯催化的一系列有机氯化物和溴化物与双官能C（sp 3）-（三甲基甲硅烷基）甲基锂试剂的直接交叉偶联。使用Pd-PEPPSI-IPent作为催化剂可以在温和的条件下（室温）以较短的反应时间高产率地制备结构多样且合成上通用的苄基和烯丙基硅烷。