(S)-methyl 3,4-xylyl sulfoxide

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (S)-methyl 3,4-xylyl sulfoxide
• 英文别名: methyl 3,4-xylyl sulfoxide；1,2-dimethyl-4-[(S)-methylsulfinyl]benzene
• 化学式: C₉H₁₂OS
• 分子量: 168.26
• InChiKey: ICPICMYTXUBOQA-NSHDSACASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 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：
  36.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  1,2-Dimethyl-4-(methylthio)benzene 在 叔丁基过氧化氢 、 iron(III) sulfate 、 (R,R)-N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediamine 作用下， 以 水 为溶剂， 反应 2.0h， 以92%的产率得到(S)-methyl 3,4-xylyl sulfoxide
  参考文献：
  名称：

  Fe（III）催化剂氧化硫化物的新方法

  摘要：

  在催化量的Fe 2（SO 4）3存在下，多种硫化物以70％t- BuOOH（水）为氧化剂转化为相应的亚砜衍生物。所描述的方法具有广泛的应用范围，涉及简单的后处理，具有化学选择性/对映选择性，并且可以在温和的反应条件下进行。在合理的时间内以高收率获得所得产物。版权所有©2012 John Wiley＆Sons，Ltd.

  DOI：

  10.1002/aoc.1859

文献信息

• Probing the scope of the sulfoxidation activity of vanadium bromoperoxidase from Ascophyllum nodosum
  作者：Hilda B ten Brink、Herbert L Holland、Hans E Schoemaker、Hester van Lingen、Ron Wever

  DOI：10.1016/s0957-4166(99)00514-5

  日期：1999.12

  the corresponding sulfide in the presence of hydrogen peroxide. Investigation of the sulfoxidation activity of this enzyme shows that activating substituents at the para-position of the aromatic ring of methyl phenyl sulfide positively influence the selectivity of the reaction, whereas strongly electron-withdrawing groups cancel the catalyzed sulfoxidation reaction. The first evidence is presented that

  先前已经表明，来自结壳菌的钒溴过氧化物酶介导在过氧化氢存在下由相应的硫化物产生具有91％对映体过量的（R）-甲基苯基亚砜。对这种酶的硫氧化活性的研究表明，在甲基苯基硫醚的芳环对位的活化取代基对反应的选择性产生积极影响，而强吸电子基团则取消了催化的硫氧化反应。提出的第一个证据是钒溴过氧化物酶以高动力学分辨率催化外消旋非芳族环状硫醚的硫氧化反应。
• Enantioselective Inclusion of Methyl Phenyl Sulfoxides and Benzyl Methyl Sulfoxides by (<i>R</i>)-Phenylglycyl-(<i>R</i>)-phenylglycine and the Crystal Structures of the Inclusion Cavities
  作者：Motohiro Akazome、Yuki Ueno、Haruko Ooiso、Katsuyuki Ogura

  DOI：10.1021/jo991051l

  日期：2000.1.1

  Crystalline (R)-phenylglycyl-(R)-phenylglycine [(R,R)-1] includes methyl phenyl sulfoxides (2 and 3) and benzyl methyl sulfoxides (4) with high enantioselectivity. The dipeptide exhibited different stereoselectivity depending on four structural isomers of methyl tolyl sulfoxide (C8H10OS): R for methyl 2-tolyl sulfoxide, S for methyl 3-tolyl sulfoxide, and racemic for methyl 4-tolyl sulfoxide. A structural isomer, benzyl methyl sulfoxide, was included in racemic form. Chlorophenyl methyl sulfoxides 3 (C7H7ClOS) with a similar volume showed the same enantioselectivity for their recognition. By single-crystal X-ray analyses of these inclusion compounds, it was elucidated that (R,R)-1 molecules self-assembled to form layer structures and included the sulfoxides between these layers and that the origin of the enantioselectivity based on chiral cavities was induced by conformation of the C-terminal phenyl group of the dipeptide. The relative position between the ammonio proton and the C-terminal phenyl group in one molecule of the dipeptide determined the stereochemistry of the methyl sulfinyl groups to be recognized. Various positional isomers of methyl xylyl sulfoxide having the formula of C9H12OS were subjected to the enantioselective inclusion by (R,R)-1 crystals and these results are also discussed.
• Predominant (<i>S</i>)-Enantioselective Inclusion of Aryl Methyl Sulfoxides by (<i>S</i>)-Isoleucyl-(<i>S</i>)-phenylglycines
  作者：Motohiro Akazome、Ai Doba、Shoji Matsumoto、Katsuyuki Ogura

  DOI：10.1021/jo902197k

  日期：2010.2.5

  In terms of chiral recognition for racemic aryl methyl sulfoxides in the solid state, three kinds of crystalline (S)-alkylglycyl-(S)-phenylglycines were examined as potential dipeptides host molecules. When (S)-alanyl-(S)-phenylglycines [(S,S)-Ala-Phg] crystallized with aryl methyl sulfoxides, the stereochemistry of preferentially included sulfoxides depended on the individual shapes of the sulfoxides and the enantiomeric excess was relatively low. Although (S)-leucyl-(S)phenylglycines [(S,S)-Leu-Phg] and (S)-isoleucyl-(S)-phenylglycines [(S,S)-Ile-Phg] mainly included the S-form of aryl methyl sulfoxides, the enantiomeric recognition of (S,S)-Ile-Phg was superior to that of (S,S)-Leu-Phg. Single-crystal X-ray analysis of these inclusion compounds revealed that the dipeptide molecules self-assembled to form layer structures and included sulfoxides between these layers through hydrogen bonding between the proton of (+)NH(3) and the oxygen of the sulfoxide. Besides these host-guest interactions, the phenyl groups of the sulfoxides interacted with each other through the phenyl-phenyl interaction. Two adjacent homochiral sulfoxides make a pair having a 2-fold screw axis along the channel cavity. Thus, the self-recognition of sulfoxides made 2(1) helical column structures and had high enantioselectivity.
• A new methodology for the oxidation of sulfides with Fe(III) catalysts
  作者：Debashis Chakraborty、Payal Malik、Vinod Kumar Goda

  DOI：10.1002/aoc.1859

  日期：2012.1

  A variety of sulfides were converted to the corresponding sulfoxide derivatives with 70% t‐BuOOH (water) as the oxidant in the presence of catalytic quantity of Fe2(SO4)3. The method described has a wide range of applications, involves simple work‐up, exhibits chemoselectivity/enantioselectivity and proceeds under mild reaction conditions. The resulting products are obtained in good yield within a

  在催化量的Fe 2（SO 4）3存在下，多种硫化物以70％t- BuOOH（水）为氧化剂转化为相应的亚砜衍生物。所描述的方法具有广泛的应用范围，涉及简单的后处理，具有化学选择性/对映选择性，并且可以在温和的反应条件下进行。在合理的时间内以高收率获得所得产物。版权所有©2012 John Wiley＆Sons，Ltd.