2-trimethylsilylbenzenethiol | 33356-45-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯硫酚类
• 英文名称: 2-trimethylsilylbenzenethiol
• 英文别名: 2-(trimethylsilyl)thiophenol；Trimethylsilylbenzenethiol
• CAS: 33356-45-5
• 化学式: C₉H₁₄SSi
• 分子量: 182.362
• InChiKey: PFLIPGRNNMWXEB-UHFFFAOYSA-N

物化性质

• 沸点：
  228.7±23.0 °C(Predicted)
• 密度：
  0.96±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.52
• 重原子数：
  11
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  1
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2-trimethylsilylbenzenethiol 在 三氟甲磺酸 、 2-TMSC₆H₄SLi 、 (-)-(1R,2R)-1-dimethylamino-2-(2-methoxyphenoxy)-1,2-diphenylethane 作用下， 以 正己烷 、 甲苯 为溶剂， 反应 120.17h， 生成 (S)-methyl 3-phenylthiobutanoate
  参考文献：
  名称：

  Steric Tuning of Reactivity and Enantioselectivity in Addition of Thiophenol to Enoates Catalyzed by an External Chiral Ligand

  摘要：

  DOI：

  10.1021/ja9729950
• 作为产物：
  描述：

  2-(trimethylsilyl)phenyl trimethylsilyl ether 在 盐酸 、 lithium aluminium tetrahydride 、 sodium hydride 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 生成 2-trimethylsilylbenzenethiol
  参考文献：
  名称：

  Synthetic equivalents of benzenethiol and benzyl mercaptan having faint smell: odor reducing effect of trialkylsilyl group

  摘要：

  Syntheses and odor tests of the trialkylsilylated benzyl mercaptans and benzenethiols have revealed that the trimethylsilyl substituent on the benzene ring has a remarkable effect in reducing the foul smell of the parent benzyl mercaptan and benzenethiol. Protodesilylation allowed these silylated thiols to function as odorless synthetic equivalents of benzyl mercaptan and benzenethiol. This discovery will greatly improve the physical environment of the researcher working with these malodorous compounds. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(02)02052-x

文献信息

• Catalytic Enantioselective Protonation of Lithium Ester Enolates Generated by Conjugate Addition of Arylthiolate to Enoates
  作者：Katsumi Nishimura、Masashi Ono、Yasuo Nagaoka、Kiyoshi Tomioka

  DOI：10.1002/1521-3773(20010119)40:2<440::aid-anie440>3.0.co;2-a

  日期：2001.1.19

  A chiral ligand, a catalytic amount of lithium cation, and no chiral proton source: These are features of the present asymmetric addition-protonation of propenoates with 2-trimethylsilylbenzenethiol. The reaction is catalyzed by a combination of lithium 2-trimethylsilylbenzenethiolate and the chiral ligand 1. Desulfurization of the product affords 2-substituted propanoates with high ee values and without

  手性配体，催化量的锂阳离子和无手性质子源：这些是本酸酯与2-三甲基甲硅烷基苯硫醇的不对称加成质子化的特征。该反应由2-三甲基甲硅烷基苯硫醇锂和手性配体1的组合催化。产物的脱硫得到具有高ee值且没有外消旋作用的2-取代的丙酸酯。此外，可以定量地回收1以便重新使用。
• An Effective and Selective Synthesis of Sterically Crowded Benzotrithioles from Benzodithiastannoles via Benzotrithiole 2-Oxides
  作者：Satoshi Ogawa、Naoki Yomoji、Shin-ichi Chida、Ryu Sato

  DOI：10.1246/cl.1994.507

  日期：1994.3

  Sterically crowded benzotrithioles were efficiently and selectively prepared by the reduction of corresponding benzotrithiole 2-oxides which were readily obtained on treatment of benzodithiastannoles, synthetic equivalents of benzenedithiols, with thionyl chloride.

  通过将相应的苯并三硫醇2-氧化物还原，可以高效且选择性地制备空间拥挤的苯并三硫醇，而这些苯并三硫醇2-氧化物是通过用亚硫酰氯处理苯并二硫锡烷（苯并二硫醇的合成等价物）轻松获得的。
• Development of Odorless Thiols and Sulfides and Their Applications to Organic Synthesis
  作者：Kiyoharu Nishide、Shin-ichi Ohsugi、Tetsuo Miyamoto、Kamal Kumar、Manabu Node

  DOI：10.1007/s00706-003-0122-1

  日期：2004.2.1

  Development of new odorless thiols (dodecanethiol, 4- n -heptylphenylmethanethiol, 4-trimethylsilylphenylmethanethiol, 4-trimethylsilylbenzenethiol) and an odorless sulfide (1-methylsulfanyldodecane) and their applications to dealkylation, Michael addition, Swern oxidation, and Corey - Kim oxidation are described.

  描述了新型无味硫醇（十二烷硫醇，4- 正 庚基苯基甲硫醇，4-三甲基甲硅烷基苯基甲硫醇，4-三甲基甲硅烷基苯硫醇）和无味硫化物（1-甲基硫烷基十二烷 ）的开发及其在脱烷基， 迈克尔 加成， Swern 氧化和 科里 - 金 氧化中的应用。 。
• Chiral Amino Ether-Controlled Catalytic Enantioselective Arylthiol Conjugate Additions to α,β-Unsaturated Esters and Ketones:  Scope, Structural Requirements, and Mechanistic Implications
  作者：Katsumi Nishimura、Kiyoshi Tomioka

  DOI：10.1021/jo015879v

  日期：2002.1.1

  Asymmetric conjugate addition reaction of 2-trimethylsilylbenzenethiol with enoates and enones is catalyzed by a chiral amino ether-lithium thiolate complex and affords adducts with high enantioselectivity. Both the s-cis conformation and a steric wall at one side of the carbonyl group are structural requirements in substrates yielding adducts with high enantioselectivity. Reactions with tert-butyl

  手性氨基醚-硫醇锂络合物催化2-三甲基甲硅烷基苯硫醇与烯酸酯和烯酮的不对称共轭加成反应，并提供高对映选择性的加合物。s-顺式构象和羰基一侧的空间壁都是底物的结构要求，这些底物产生具有高对映选择性的加合物。与叔丁基烯酮的反应得到具有高对映选择性的加成产物。通过该加成-质子化序列可以构建两个连续的手性中心。钛酸甲酯被立体选择性地转化为带有两个连续手性中心的单一的95％对映体过量（ee）的合成加合物。将2-苯基-2-丁烯酸甲酯转化为单一的95％ee的加合物，然后将其脱硫为95％ee的2-苯基丁酸甲酯。
• Catalytic Intramolecular Acylsulfenylation of Activated Alkenes: Enantioselective Synthesis of 3,3-Disubstituted Quinoline-2,4-diones
  作者：Wei Liu、Huan-Qing Zhang、Wei-Wei Liao

  DOI：10.1021/acscatal.8b01412

  日期：2018.6.1

  asymmetric intramolecular acylsulfenylation approach is presented. By combining catalytic amount of chiral amino diether (1S,2S)-L6 and RSLi, a wide range of 3,3-disubstituted quinoline-2,4-dione derivatives incorporating all-carbon quaternary stereocenters could be accessed in excellent yields and enantioselectivities in a catalytically atom-economic fashion. The concept relies on an asymmetric SMA/aldol type

  提出了一种不对称的分子内酰基磺酰化方法。通过组合的催化量的手性氨基二醚（1 S， 2小号） - L6和RSLI，广泛包含全碳季立体3,3-二取代的喹啉-2,4-二酮衍生物的能以优良产率访问和催化原子经济方式的对映选择性。通过使用硫酯作为双功能羰基资源，该概念依赖于不对称SMA /羟醛类型序列，这使环状支架的构建得以顺利进行。