(S)-2-(methylsulfinyl)benzimidazole

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并咪唑类
• 英文名称: (S)-2-(methylsulfinyl)benzimidazole
• 英文别名: 2-methyl(sulfinyl)benzimidazole；2-[(S)-methylsulfinyl]-1H-benzimidazole
• 化学式: C₈H₈N₂OS
• 分子量: 180.23
• InChiKey: KWUOZCQDBYFKRM-LBPRGKRZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  12.0
• 可旋转键数：
  1.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  45.75
• 氢给体数：
  1.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  (S)-2-(methylsulfinyl)benzimidazole 、 1-溴-三氟对二甲苯 在 N,N,N,N-tetraethylammonium tetrafluoroborate 、 1-butyl-3-methylimidazolium Tetrafluoroborate 作用下， 以 乙腈 为溶剂， 生成 2-(methylsulfinyl)-N-(4-trifluoromethyl)benzyl-benzimidazole
  参考文献：
  名称：

  手性 2-(甲基亚磺酰基) 1H-苯并咪唑的电化学诱导 N-烷基化

  摘要：

  摘要 手性 2-(甲基亚磺酰基) 1H-苯并咪唑在乙腈/四氟硼酸四乙基铵体系中的恒电流电解已被用来进行苯并咪唑部分与有机卤化物的选择性 N-烷基化，从而获得在药物研究中具有潜在用途的手性衍生物。已对标题化合物的氧化还原电位进行了理论测定，并描述了其电活化的合理途径。此外，通过这种电化学策略，已经建立了获得对映体富集的 N-烷基化 2-（甲基亚磺酰基）苯并咪唑的途径。图形概要

  DOI：

  10.1080/00397911.2015.1044616
• 作为产物：
  描述：

  2-(甲基硫代)苯并咪唑 在 titanium(IV) isopropylate 、 D-(-)-酒石酸二乙酯 过氧化氢异丙苯 、 N,N-二异丙基乙胺 作用下， 以 水 、 甲苯 为溶剂， 反应 2.75h， 以65%的产率得到(S)-2-(methylsulfinyl)benzimidazole
  参考文献：
  名称：

  Factors influencing the selectivity in asymmetric oxidation of sulfides attached to nitrogen containing heterocycles

  摘要：

  使用酒石酸/钛（iOPr）4 催化剂体系研究了杂环硫化物（包括咪唑、苯并咪唑、吲哚和嘧啶衍生物）的不对称氧化。

  DOI：

  10.1039/b700860k

文献信息

• Factors influencing the selectivity in asymmetric oxidation of sulfides attached to nitrogen containing heterocycles
  作者：Muthu Seenivasaperumal、Hans-J?rgen Federsel、Anne Ertan、K?lm?n J. Szab?

  DOI：10.1039/b700860k

  日期：——

  Asymmetric oxidation of heterocyclic sulfides, including imidazole, benzimidazole, indole and pyrimidine derivatives, were studied using a tartrate/Ti(iOPr)4 catalyst system.

  使用酒石酸/钛（iOPr）4 催化剂体系研究了杂环硫化物（包括咪唑、苯并咪唑、吲哚和嘧啶衍生物）的不对称氧化。
• Electrochemically Induced N-Alkylation of Chiral 2-(Methylsulfinyl) 1H-Benzimidazole
  作者：Amedeo Capobianco、Tonino Caruso、Laura Palombi

  DOI：10.1080/00397911.2015.1044616

  日期：2015.8.3

  Abstract Galvanostatic electrolysis of chiral 2-(methylsulfinyl) 1H-benzimidazole in an acetonitrile/tetraethyl ammonium tetrafluoroborate system has been exploited to carry out the selective N-alkylation of the benzimidazole moiety with organohalides, thus obtaining chiral derivatives with potential use in drug research. Theoretical determination of the redox potential for the title compound has been

  摘要 手性 2-(甲基亚磺酰基) 1H-苯并咪唑在乙腈/四氟硼酸四乙基铵体系中的恒电流电解已被用来进行苯并咪唑部分与有机卤化物的选择性 N-烷基化，从而获得在药物研究中具有潜在用途的手性衍生物。已对标题化合物的氧化还原电位进行了理论测定，并描述了其电活化的合理途径。此外，通过这种电化学策略，已经建立了获得对映体富集的 N-烷基化 2-（甲基亚磺酰基）苯并咪唑的途径。图形概要
• Mechanism of the Asymmetric Sulfoxidation in the Esomeprazole Process: Effects of the Imidazole Backbone for the Enantioselection
  作者：Muthu Seenivasaperumal、Hans-Jürgen Federsel、Kálmán J. Szabó

  DOI：10.1002/adsc.200800753

  日期：2009.4

  Abstractmagnified imageThe asymmetric sulfoxidation reaction of imidazole‐based prochiral sulfides was studied to explore the mechanistic details of the highly efficient esomeprazole process, which is one of the few industrial scale catalytic asymmetric procedures. The synthetic studies revealed that the smallest subunit governing the selectivity in the esomeprazole process is an imidazole ring. Thus, by using the esomeprazole procedure methyl imidazole sulfide could be oxidized as efficiently as its several functionalized derivatives, including pyrmetazol. However, alkylation of the imidazole nitrogen led to a major drop of the enantioselectivity. Our atmospheric pressure chemical ionization‐mass spectrometry (APCI/MS) studies indicate that addition of small amounts of water to the reaction mixture facilitates the formation of mononuclear titanium species, which are the active catalytic intermediates of the selective oxidation reaction. One of the most important features of the esomeprazole procedure is that amine additives increase the enantioselectivity of the oxidation process. The NMR studies of the presumed reaction intermediates show that under catalytic conditions the amines are able to coordinate to titanium and dissociate the coordinated imidazole substrate. The density functional theory (DFT) modelling studies provided new insights in the mechanism of the asymmetric induction. It was found that the oxidation requires a lower activation energy if the imidazole sulfide precursor does not coordinate to titanium. Two possible reaction paths were explored for this out of sphere oxidation mechanism. The most important interaction governing the enantioselection is hydrogen bonding between the NH of the imidazole ring and the chiral tartrate ligand on titanium. Furthermore, the oxidation reaction imposes an important structural constraint to the TS structure involving a linear arrangement of the peroxide oxygens and the sulfur atom. This constraint and the N coordination of imidazole leads to a very strained structure for the inner sphere mechanism of the oxidation, which leads to a much higher activation barrier than the corresponding out of sphere process, and therefore it is unlikely.