bis(2-hydroxymethylphenyl)sulfoxide | 63743-97-5

• 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: bis(2-hydroxymethylphenyl)sulfoxide
• 英文别名: Bis-<2-(hydroxymethyl)phenyl>sulfoxid；Bis-[2-(hydroxymethyl)phenyl]sulfoxid；[2-[2-(Hydroxymethyl)phenyl]sulfinylphenyl]methanol
• CAS: 63743-97-5
• 化学式: C₁₄H₁₄O₃S
• 分子量: 262.329
• InChiKey: LAWUVKLZLOBSQQ-UHFFFAOYSA-N

物化性质

• 熔点：
  125-127 °C
• 沸点：
  532.1±45.0 °C(Predicted)
• 密度：
  1.39±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  76.7
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  bis(2-hydroxymethylphenyl)sulfoxide 在 三乙胺 作用下， 以 二氯甲烷 、 氯仿 为溶剂， 反应 24.75h， 生成 bis[N-(S)-prolinylmethylphenyl]sulfoxide
  参考文献：
  名称：

  Highly efficient chiral polydentate sulfinyl ligands/catalysts containing prolinol moiety

  摘要：

  New polydentate chiral ligands, containing the hydroxyl group, stereogenic sulfinyl group and enantiomeric prolinol moieties were synthesized and proved very efficient catalysts in the asymmetric diethylzinc addition to benzaldehyde, the asymmetric aldol condensation and the asymmetric Mannich reaction. Replacement of the central hydroxyl group with the second prolinol moiety of the same absolute configuration gave new ligands in which the sulfinyl group was not a stereogenic centre anymore, but which proved almost equally efficient as catalysts for the reactions investigated. The absolute configuration of the proline moiety exerted a decisive impact on the stereochemical outcome of these reactions, deciding about the absolute configuration of the products formed. (C) 2015 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2015.05.103
• 作为产物：
  描述：

  2-(tetrahydropyranyloxy)methylbromobenzene 在 4-甲基苯磺酸吡啶 、 magnesium 作用下， 以 四氢呋喃 、 乙醇 为溶剂， 反应 28.0h， 生成 bis(2-hydroxymethylphenyl)sulfoxide
  参考文献：
  名称：

  Highly efficient chiral polydentate sulfinyl ligands/catalysts containing prolinol moiety

  摘要：

  New polydentate chiral ligands, containing the hydroxyl group, stereogenic sulfinyl group and enantiomeric prolinol moieties were synthesized and proved very efficient catalysts in the asymmetric diethylzinc addition to benzaldehyde, the asymmetric aldol condensation and the asymmetric Mannich reaction. Replacement of the central hydroxyl group with the second prolinol moiety of the same absolute configuration gave new ligands in which the sulfinyl group was not a stereogenic centre anymore, but which proved almost equally efficient as catalysts for the reactions investigated. The absolute configuration of the proline moiety exerted a decisive impact on the stereochemical outcome of these reactions, deciding about the absolute configuration of the products formed. (C) 2015 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2015.05.103

文献信息

• Enzyme-promoted desymmetrization of bis(2-hydroxymethylphenyl) sulfoxide as a route to tridentate chiral catalysts
  作者：Michał Rachwalski、Małgorzata Kwiatkowska、Józef Drabowicz、Marcin Kłos、Wanda M. Wieczorek、Małgorzata Szyrej、Lesław Sieroń、Piotr Kiełbasiński

  DOI：10.1016/j.tetasy.2008.08.017

  日期：2008.9

  The desymmetrization of prochiral bis(2-hydroxymethylphenyl) sulfoxide 3 was efficiently performed via acetylation promoted by commonly available lipases. Two lipases, namely, CAL-B and LPL proved particularly efficient to give 2-acetoxymethylphenyl 2-hydroxymethylphenyl sulfoxide 4 in up to 98% yield and with up to 98% ee. On the basis of an X-ray analysis, the absolute configuration of 4 was determined

  前手性双（2-羟甲基苯基）亚砜3的去对称化是通过通常可获得的脂肪酶促进的乙酰化而有效地进行的。两种脂肪酶，即CAL-B和LPL被证明特别有效地以高达98％的收率和高达98％的ee生成2-乙酰氧基甲基苯基2-羟甲基苯基亚砜4。根据X射线分析，将4的绝对构型确定为（+）-（R）。然后将对映体纯的产物4转化为一系列对映体纯的非对映体2-氨基甲基苯基2-羟甲基苯基亚砜8其中氨基源自具有附加的C-立体异构中心的对映体纯的胺。在二乙基锌与苯甲醛的参比反应中，以尽可能高的收率和高达50％的ee值，将化合物8作为三齿手性催化剂作为可能的三齿手性催化剂进行了研究。
• Efficient catalysts for asymmetric Mannich reactions
  作者：Michał Rachwalski、Tim Leenders、Sylwia Kaczmarczyk、Piotr Kiełbasiński、Stanisław Leśniak、Floris P. J. T. Rutjes

  DOI：10.1039/c3ob40681d

  日期：——

  Efficient chiral catalysts for direct asymmetric three-component Mannich reactions of ketones, aldehydes and an amine (p-anisidine) have been developed. The corresponding β-amino carbonyl compounds (Mannich adducts) were obtained in good chemical yields and excellent enantio- and diastereoselectivities. The reaction conditions have been optimized by invoking ultrasonication and the influence of some structural moieties of the catalysts on the chemical yield and stereoselectivity of the Mannich products has been evaluated.

  针对酮、醛和胺（对甲氧基苯胺）的直接不对称三组分曼尼希反应开发了高效手性催化剂。获得了相应的 β-氨基羰基化合物（曼尼希加合物），化学收率高，对映和非对映选择性极佳。通过使用超声波对反应条件进行了优化，并评估了催化剂的某些结构分子对曼尼希产物的化学收率和立体选择性的影响。
• Highly enantioselective Henry reaction catalyzed by chiral tridentate heteroorganic ligands
  作者：Michał Rachwalski、Stanisław Leśniak、Ewelina Sznajder、Piotr Kiełbasiński

  DOI：10.1016/j.tetasy.2009.06.015

  日期：2009.7

  New tridentate enantiomerically pure heteroatom catalysts, containing hydroxyl, sulfinyl and amino groups, proved to be highly efficient in the enantioselective nitroaldol (Henry) reaction to give the desired adducts in very high yields (Lip to 90%) and with ees up to 98%. The influence of the stereogenic centres located on the sulfinyl sulfur atom and in the amine moiety is also discussed. (C) 2009 Elsevier Ltd. All rights reserved.