(2,4-dimethylphenyl)methylsulfoxide | 211310-44-0

• 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: (2,4-dimethylphenyl)methylsulfoxide
• 英文别名: methyl 2,4-xylyl sulfoxide；2,4-Dimethyl-1-methylsulfinylbenzene
• CAS: 211310-44-0
• 化学式: C₉H₁₂OS
• 分子量: 168.26
• InChiKey: FCJIAOMKFLCKAZ-UHFFFAOYSA-N

物化性质

• 沸点：
  300.2±31.0 °C(Predicted)
• 密度：
  1.12±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 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

• 作为反应物：
  描述：

  (2,4-dimethylphenyl)methylsulfoxide 在 间氯过氧苯甲酸 、 三氟乙酸酐 作用下， 以 二氯甲烷 为溶剂， 反应 0.5h， 生成 4-[(2,4-Dimethyl)phenylsulfinyl]-2,3-dihydrofuran
  参考文献：
  名称：

  Sulfoxides as Stereochemical Controllers in Intermolecular Heck Reactions

  摘要：

  The study of a variety of substituted sulfoxides as chiral auxiliaries in intermolecular Heck reactions of sulfinyldihydrofurans and sulfinylcyclopentenes with different iodoarenes is reported. In the presence of [Pd(OAc)(2)]/Ag2CO3 and a bidentate phosphine ligand, synthetically useful yields and asymmetric inductions were obtained. By far the best diastereoselectivities were obtained by the use of the palladium-coordinating o-(N,N-dimethylamino)phenylsulfinyl group. By final removal of the chiral auxiliary, these sulfoxide-stereocontrolled asymmetric Heck processes were applied to the enantioselective synthesis of 1-aryl-substituted and 1,3-diaryl-substituted dihydrofurans and cyclopentenes.

  DOI：

  10.1002/1521-3765(20010917)7:18<3890::aid-chem3890>3.0.co;2-y
• 作为产物：
  描述：

  methyl 2,4-dimethylphenyl sulphide 在 间氯过氧苯甲酸 作用下， 生成 (2,4-dimethylphenyl)methylsulfoxide
  参考文献：
  名称：

  通过新的恶唑烷鎓盐将硫化物高度对映选择性氧化为亚砜。

  摘要：

  新的恶二氮杂鎓盐5（R2 = TBDPS）是有效的试剂，用于将硫化物高度对映体选择性氧化为亚砜，ee最高可达99％以上，且收率很高。因此，它代表了现有的不对称硫氧化方法的一种新的有价值的非金属替代品。

  DOI：

  10.1021/ol0702573

文献信息

• Systematic Evaluation of Sulfoxides as Catalysts in Nucleophilic Substitutions of Alcohols
  作者：Sebastian Motsch、Christian Schütz、Peter H. Huy

  DOI：10.1002/ejoc.201800907

  日期：2018.9.9

  Out of an in‐depth study of a range of sulfinyl compounds in the transformation of alcohols into chloro alkanes emerged (2‐methoxyphenyl)methyl sulfoxide as optimal Lewis base catalyst. While this catalyst allowed the synthesis of benzylic chlorides in turn‐over numbers up to 50, aliphatic alcohols are non‐suitable substrates due to competing Pummerer rearrangement.

  在深入研究一系列亚砜基化合物将醇转化为氯代烷烃的过程中，出现了（2-甲氧基苯基）甲基亚砜作为最佳的路易斯碱催化剂。尽管该催化剂可以合成多达50个转换量的苄基氯，但由于竞争的Pummerer重排，脂肪族醇不适合作为底物。
• Symmetric Diarylsulfoxides as Asymmetric Sulfinylating Reagents for Dialkylmagnesium Compounds
  作者：Simon Ruppenthal、Reinhard Brückner

  DOI：10.1021/jo502417j

  日期：2015.1.16

  dilithium salt of (S)-BINOL was added as a promotor. Alkyl aryl sulfoxides resulted in up to quantitative yield and with up to 97% ee. This demonstrates the feasibility of asymmetric sulfinylations by achiral sulfinylating agents (from the perspective of Alkyl2Mg) as well as the feasibility of asymmetric sulfoxide–magnesium exchanges (from the perspective of Ar2SO).

  在-78°C下，当添加1.5当量的（S）-BINOL二锂盐作为促进剂时，伯二烷基镁化合物与二芳基亚砜反应。烷基芳基亚砜导致定量产率最高，ee高达97％。这证明了通过非手性亚磺化剂进行不对称亚磺酰基化的可行性（从烷基2 Mg的角度来看），以及不对称亚砜与镁交换的可行性（从Ar 2 SO角度来看）。
• Discovery and Rational Mutagenesis of Methionine Sulfoxide Reductase Biocatalysts To Expand the Substrate Scope of the Kinetic Resolution of Chiral Sulfoxides
  作者：Silvia Anselmi、Alexandra T. P. Carvalho、Angela Serrano-Sanchez、Jose L. Ortega-Roldan、Jill Caswell、Iman Omar、Gustavo Perez-Ortiz、Sarah M. Barry、Thomas S. Moody、Daniele Castagnolo

  DOI：10.1021/acscatal.3c00372

  日期：——

  enzymes has been designed via rational mutagenesis utilizing in silico docking, molecular dynamics, and structural nuclear magnetic resonance (NMR) studies. The mutant enzyme MsrA33 was found to catalyze the kinetic resolution of bulky sulfoxide substrates bearing non-methyl substituents on the sulfur atom with ees up to 99%, overcoming a significant limitation of the currently available MsrA biocatalysts

  甲硫氨酸亚砜还原酶 A (MsrA) 酶最近在外消旋亚砜的对映选择性动力学分辨率中发现了作为非氧化生物催化剂的应用。这项工作描述了选择性和稳健的 MsrA 生物催化剂的鉴定，这些催化剂能够在 8–64 mM 浓度下催化各种芳香族和脂肪族手性亚砜的对映选择性还原，并具有高产率和出色的 ee（高达 99%）。此外，为了扩大 MsrA 生物催化剂的底物范围，已经通过计算机合理诱变设计了一个突变酶库对接、分子动力学和结构核磁共振 (NMR) 研究。发现突变酶 MsrA33 可催化硫原子上带有非甲基取代基的庞大亚砜底物的动力学拆分，ees 高达 99%，克服了目前可用的 MsrA 生物催化剂的重大局限性。
• 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.
• Sulfoxides as Stereochemical Controllers in Intermolecular Heck Reactions
  作者：Nuria Díaz Buezo、Juan Carlos de la Rosa、Julián Priego、Inés Alonso、Juan Carlos Carretero

  DOI：10.1002/1521-3765(20010917)7:18<3890::aid-chem3890>3.0.co;2-y

  日期：2001.9.17

  The study of a variety of substituted sulfoxides as chiral auxiliaries in intermolecular Heck reactions of sulfinyldihydrofurans and sulfinylcyclopentenes with different iodoarenes is reported. In the presence of [Pd(OAc)(2)]/Ag2CO3 and a bidentate phosphine ligand, synthetically useful yields and asymmetric inductions were obtained. By far the best diastereoselectivities were obtained by the use of the palladium-coordinating o-(N,N-dimethylamino)phenylsulfinyl group. By final removal of the chiral auxiliary, these sulfoxide-stereocontrolled asymmetric Heck processes were applied to the enantioselective synthesis of 1-aryl-substituted and 1,3-diaryl-substituted dihydrofurans and cyclopentenes.