9-(methylsulfinyl)phenanthrene

• 分子结构分类: 有机化合物 - 苯类化合物 - 菲及其衍生物
• 英文名称: 9-(methylsulfinyl)phenanthrene
• 英文别名: 9-Methylsulfinylphenanthrene
• 化学式: C₁₅H₁₂OS
• 分子量: 240.326
• InChiKey: FMICSWWXSVBSHM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  17
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.07
• 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：

  9-(methylsulfinyl)phenanthrene 在 Pd(opiv)2 、 碘苯二乙酸 、 双联邻苯二酚硼酸酯 作用下， 以 甲苯 为溶剂， 反应 8.0h， 生成 10-(methylsulfanyl)-1-(2,2,2-trifluoroethoxy)phenanthrene
  参考文献：
  名称：

  B2cat2介导的亚砜还原为硫化物

  摘要：

  描述了使用双（邻苯二酚）二硼作为还原剂将亚砜还原为硫化物的有效且操作简单的方法。该用户友好型方案的特点是高官能团耐受性和易于纯化的过程。

  DOI：

  10.1002/ejoc.202000222
• 作为产物：
  描述：

  9-溴菲 在 双氧水 、 叔丁基锂 作用下， 以 乙醚 、 正己烷 、 丙酮 为溶剂， 反应 10.5h， 生成 9-(methylsulfinyl)phenanthrene
  参考文献：
  名称：

  Photophysics and Photostereomutation of Aryl Methyl Sulfoxides¹

  摘要：

  The effect of a methanesulfinyl group on the photophysics of several aromatic chromophores is reported. The spectroscopic singlet and triplet energies are affected only modestly, compared to that parent arenes, but the fluorescence yields fall by at least 1 order of magnitude. Fluorescence lifetimes are short. Fluorescence enhancements are observed on cooling the sulfoxides from room temperature to 77 K. High quantum yields of stereomutation are reduced as the temperature drops. There is not a consistent effect on triplet or phosphorescence yields. It is proposed that these results are consistent with a nonradiative pathway for deactivation of the singlet that results in stereomutation. A modest activation energy of a few kcal/mol is estimated for the photochemical racemization of 1-methanesulfinylpyrene

  DOI：

  10.1021/jo0056141

文献信息

• Palladium‐Catalyzed <i>peri</i> ‐Selective C−H Fluoroalkoxylation of Aryl Sulfoxides
  作者：Tomohiko Sato、Keisuke Nogi、Hideki Yorimitsu

  DOI：10.1002/cctc.202000485

  日期：2020.7.6

  Sulfinyl‐directed peri‐selective C−H fluoroalkoxylation of aryl sulfoxides with fluorinated alcohols has been developed. By means of a palladium catalyst and PhI(OAc)2 as an oxidant, a range of fluoroalkoxy groups can be installed onto the peri position of aryl sulfoxides. The remaining sulfinyl groups on the fluoroalkoxylation products further promote Pummerer‐based C−H functionalizations.

  亚磺酰定向围与氟化醇芳基亚砜-选择性C-H fluoroalkoxylation已经研制成功。借助于钯催化剂和PhI（OAc）2作为氧化剂，可以将一系列的氟代烷氧基安装在芳基亚砜的周围。氟代烷氧基化产物上剩余的亚磺酰基进一步促进了基于Pummerer的CH的功能化。
• Regioselective C–H Sulfanylation of Aryl Sulfoxides by Means of Pummerer-Type Activation
  作者：Hitomi Kawashima、Tomoyuki Yanagi、Chien-Chi Wu、Keisuke Nogi、Hideki Yorimitsu

  DOI：10.1021/acs.orglett.7b02147

  日期：2017.9.1

  A regioselective C–H sulfanylation of aryl sulfoxides with alkyl aryl sulfides in the presence of acid anhydride was developed, which resulted in the formation of 1,4-disulfanylarenes after dealkylation of initially formed sulfonium salts. The reaction began with Pummerer-type activation of aryl sulfoxides followed by nucleophilic attack of alkyl aryl sulfides. The nucleophilic attack occurred exclusively

  在酸酐存在下，芳基亚砜与烷基芳基硫醚的区域选择性C–H磺酰化反应得到了发展，这导致最初形成的salts盐脱烷基后形成了1,4-二硫杂亚芳基。反应开始于芳基亚砜的Pummerer型活化，然后是烷基芳基硫醚的亲核攻击。亲核攻击只发生在对位，或者在对位不可用的情况下，在特定位置发生，这主要受亚砜导向剂的完全控制，而与任何其他取代基无关。最初形成的芳基sulf盐是可分离的，可用作钯与四芳基硼酸钠的芳基化反应的卤代芳基替代物。
• Palladium‐Catalyzed C−H Iodination of Arenes by Means of Sulfinyl Directing Groups
  作者：Hayate Saito、Keita Yamamoto、Yosuke Sumiya、Ling‐Jun Liu、Keisuke Nogi、Satoshi Maeda、Hideki Yorimitsu

  DOI：10.1002/asia.202000591

  日期：2020.8.17

  C−H iodination of aromatic compounds has been accomplished with the aid of sulfinyl directing groups under palladium catalysis. The reaction proceeds selectively at the peri‐position of polycyclic aryl sulfoxides or at the ortho‐position of phenyl sulfoxides. The iodination products can be further converted via iterative catalytic cross‐coupling at the expense of the C−I and C−S bonds. Computational

  芳族化合物的CHH碘化反应是在钯催化下借助亚磺酰基导向基团完成的。该反应在多环芳基亚砜的周边或苯基亚砜的邻位选择性进行。碘化产物可以通过迭代催化交叉偶联进一步转化，但以CI和CS键为代价。计算研究表明，围-C-H palladation将着手通过非定向的通路，其特征在于，既不之前和在过渡状态下的亚磺酰基坐标到钯的硫也不氧原子。
• B₂ cat₂ -Mediated Reduction of Sulfoxides to Sulfides
  作者：Fumiya Takahashi、Keisuke Nogi、Hideki Yorimitsu

  DOI：10.1002/ejoc.202000222

  日期：2020.5.29

  An efficient and operationally simple method for the reduction of sulfoxides to sulfides using bis(catecholato)diboron as a reducing agent is described. This user‐friendly protocol is characterized by high functional group tolerance and easy purification process.

  描述了使用双（邻苯二酚）二硼作为还原剂将亚砜还原为硫化物的有效且操作简单的方法。该用户友好型方案的特点是高官能团耐受性和易于纯化的过程。
• Photophysics and Photostereomutation of Aryl Methyl Sulfoxides¹
  作者：Woojae Lee、William S. Jenks

  DOI：10.1021/jo0056141

  日期：2001.1.1

  The effect of a methanesulfinyl group on the photophysics of several aromatic chromophores is reported. The spectroscopic singlet and triplet energies are affected only modestly, compared to that parent arenes, but the fluorescence yields fall by at least 1 order of magnitude. Fluorescence lifetimes are short. Fluorescence enhancements are observed on cooling the sulfoxides from room temperature to 77 K. High quantum yields of stereomutation are reduced as the temperature drops. There is not a consistent effect on triplet or phosphorescence yields. It is proposed that these results are consistent with a nonradiative pathway for deactivation of the singlet that results in stereomutation. A modest activation energy of a few kcal/mol is estimated for the photochemical racemization of 1-methanesulfinylpyrene