(R)-4-(methylsulfinyl)benzonitrile | 60958-04-5

• 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: (R)-4-(methylsulfinyl)benzonitrile
• 英文别名: (R)-4-cyanophenyl methyl sulfoxide；4-(methylsulfinyl)benzonitrile；4-[(R)-methylsulfinyl]benzonitrile
• CAS: 60958-04-5；97474-48-1；121405-10-5
• 化学式: C₈H₇NOS
• 分子量: 165.216
• InChiKey: ZKFYBOCMRDEHJS-LLVKDONJSA-N

物化性质

• 沸点：
  356.1±25.0 °C(Predicted)
• 密度：
  1.30±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  11
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  60.1
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  对甲硫基苯甲腈 在 C₈₈H₉₀N₂O₆P₂ 、 双氧水 、 magnesium sulfate 作用下， 以 环己烷 、 水 为溶剂， 反应 2.0h， 以92%的产率得到(R)-4-(methylsulfinyl)benzonitrile
  参考文献：
  名称：

  Activation of H₂O₂ by Chiral Confined Brønsted Acids: A Highly Enantioselective Catalytic Sulfoxidation

  摘要：

  Confined chiral Bronsted acids are shown to catalyze asymmetric oxidations of sulfides to sulfoxides with hydrogen peroxide. The wide generality and high enantioselectivity of the developed method compare even to the best metal-based systems and suggest utility in other asymmetric oxidations.

  DOI：

  10.1021/ja3035637

文献信息

• The Stereoselective Oxidation of <i>para</i> ‐Substituted Benzenes by a Cytochrome P450 Biocatalyst
  作者：Rebecca R. Chao、Ian C.‐K. Lau、Tom Coleman、Luke R. Churchman、Stella A. Child、Joel H. Z. Lee、John B. Bruning、James J. De Voss、Stephen G. Bell

  DOI：10.1002/chem.202102757

  日期：2021.10.21

  The efficient and sustainable hydroxylation, epoxidation and sulfoxidation of a wide range of benzene derivatives using an engineered variant of a bacterial cytochrome P450 enzyme is reported. These reactions were catalyzed with high activity, regioselectivity and total turnover number (up to 20,000) and in certain instances these reactions were achieved with high enanatioselectivity (up to 98 % ee

  报道了使用细菌细胞色素 P450 酶的工程变体对各种苯衍生物进行有效和可持续的羟基化、环氧化和磺化氧化。这些反应以高活性、区域选择性和总转换数（高达 20,000）催化，在某些情况下，这些反应以高对映选择性（高达 98% ee .）实现。
• Chemoenzymatic Deracemization of Chiral Sulfoxides
  作者：Vladimír Nosek、Jiří Míšek

  DOI：10.1002/anie.201805858

  日期：2018.7.26

  The highly enantioselective enzyme methionine sulfoxide reductase A was combined with an oxaziridine‐type oxidant in a biphasic setup for the deracemization of chiral sulfoxides. Remarkably, high ee values were observed with a wide range of substrates, thus providing a practical route for the synthesis of enantiomerically pure sulfoxides.

  高对映选择性酶甲硫氨酸亚砜还原酶A与恶唑烷型氧化剂组合在两相装置中，用于手性亚砜的脱硫。值得注意的 是，在多种底物上均观察到了较高的ee值，从而为合成对映体纯的亚砜提供了一条实用的途径。
• Exploring the biocatalytic scope of a bacterial flavin-containing monooxygenase
  作者：Ana Rioz-Martínez、Malgorzata Kopacz、Gonzalo de Gonzalo、Daniel E. Torres Pazmiño、Vicente Gotor、Marco W. Fraaije

  DOI：10.1039/c0ob00988a

  日期：——

  A bacterial flavin-containing monooxygenase (FMO), fused to phosphite dehydrogenase, has been used to explore its biocatalytic potential. The bifunctional biocatalyst could be expressed in high amounts in Escherichia coli and was able to oxidize indole and indole derivatives into a variety of indigo compounds. The monooxygenase also performs the sulfoxidation of a wide range of prochiral sulfides, showing moderate to good enantioselectivities in forming chiral sulfoxides.

  一种含黄素的单氧化酶（FMO）与磷酸脱氢酶融合，被用于探索其生物催化潜力。这种双功能生物催化剂能够在大肠杆菌中高量表达，并能够将吲哚及其衍生物氧化成多种靛蓝化合物。该单氧化酶还对多种前手性硫化物进行亚硫氧化，显示出中等到良好的选择性，能够形成手性亚硫氧化物。
• Hypervalent Iodine(V)-Induced Asymmetric Oxidation of Sulfides to Sulfoxides Mediated by Reversed Micelles:  Novel Nonmetallic Catalytic System
  作者：Hirofumi Tohma、Shinobu Takizawa、Hiroaki Watanabe、Yuko Fukuoka、Tomohiro Maegawa、Yasuyuki Kita

  DOI：10.1021/jo982295t

  日期：1999.5.1

  chiral hypervalent iodine reagents have been used for asymmetric induction, all of them have needed more than a stoichiometric amount of chiral reagents and have shown low enantioselectivities. The described new catalytic asymmetric oxidation using a hypervalent iodine(V) reagent, iodoxybenzene (PhIO(2)), in a cationic reversed micellar system provides the first example of a catalytic asymmetric oxidation

  尽管几种类型的手性高价碘试剂已经用于不对称诱导，但是它们全部都需要超过化学计量的手性试剂，并且显示出低的对映选择性。所描述的在阳离子反向胶束系统中使用高价碘（V）试剂碘代氧苯（PhIO（2））的新催化不对称氧化提供了硫化物催化不对称氧化成亚砜的高化学收率且中等至良好的第一个例子。不使用任何过渡金属催化剂的对映选择性。通过添加催化量的十六烷基三甲基溴化铵（CTAB）和手性酒石酸衍生物，增溶和活化PhIO（2）被发现对于提高化学和光学收率是必不可少的。
• Asymmetric Counteranion‐Directed Iron Catalysis: A Highly Enantioselective Sulfoxidation
  作者：Saihu Liao、Benjamin List

  DOI：10.1002/adsc.201200251

  日期：2012.9.17

  active and enantioselective ion‐pair sulfoxidation catalyst, consisting of an achiral iron(III)‐salen cation and a chiral phosphate counteranion, mediates the oxidization of various sulfides with high yields and enantioselectivities. The enantioselectivities observed, especially for electron‐poor substrates, represent the best results so far in manganese and iron‐salen systems. This work represents the

  由非手性铁（III）-salen阳离子和手性磷酸抗衡离子组成的高活性和对映选择性离子对硫氧化催化剂，可高产率和对映选择性地介导各种硫化物的氧化。观察到的对映选择性，特别是对于贫电子底物，是迄今为止在锰和铁salen体系中的最佳结果。这项工作代表了我们的不对称抗衡阴离子导向催化（ACDC）概念在铁催化中的首次应用。