methyl (phenyl-3-d)sulfane | 823-79-0

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: methyl (phenyl-3-d)sulfane
• 英文别名: Benzene-d, 3-(methylthio)-；1-deuterio-3-methylsulfanylbenzene
• CAS: 823-79-0
• 化学式: C₇H₈S
• 分子量: 125.199
• InChiKey: HNKJADCVZUBCPG-WFVSFCRTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  8
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  25.3
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  3-甲硫基苯硼酸 在 [Ir(dF(CF₃)ppy)₂(dtbbpy)](PF₆) 、 重水 、 叔丁基硫醇 、 奎宁环-3-醇 作用下， 以 氘代氯仿 为溶剂， 反应 24.0h， 以81%的产率得到methyl (phenyl-3-d)sulfane
  参考文献：
  名称：

  通过协同硫醇、路易斯碱和光氧化还原催化芳基硼酸去硼酸化氘化

  摘要：

  报道了一种由硫醇、路易斯碱和光氧化还原催化的协同组合介导的芳基硼酸与 D 2 O脱硼氘化的温和方法。该反应显示出广泛的底物范围、优异的氘掺入和官能团耐受性。因此，该方法对于生物活性分子和药物分子的位点选择性D标记是实用的。

  DOI：

  10.1021/acs.orglett.2c00722

文献信息

• Hydrogen‐Bond‐Donor Solvents Enable Catalyst‐Free (Radio)‐Halogenation and Deuteration of Organoborons
  作者：Yi Yang、Xinyan Gao、Xiaojun Zeng、Junbin Han、Bo Xu

  DOI：10.1002/chem.202003919

  日期：2021.1.18

  A hydrogen bond donor solvent assisted (radio)halogenation and deuteration of organoborons has been developed. The reactions exhibited high functional group tolerance and needed only an ambient atmosphere. Most importantly, compared to literature methods, our conditions are more consistent with the principals of green chemistry (e.g., metal‐free, strong oxidant‐free, more straightforward conditions)

  已经开发了氢键供体溶剂辅助的有机硼的（放射性）卤化和氘代。该反应表现出高的官能团耐受性并且仅需要环境气氛。最重要的是，与文献方法相比，我们的条件与绿色化学原理更加一致（例如，无金属，无强氧化剂，更简单的条件）。
• Ion-neutral complex formation and hydrogen-shifts in the alkene loss from ionized alkyl phenyl thioethers in the gas phase
  作者：Margot W. Van Amsterdam、Steen Ingemann、Nico M. M. Nibbering

  DOI：10.1002/jms.1190300109

  日期：1995.1

  The mechanistic aspects of alkene loss from ionized ethyl-and n-propyl phenyl thioethers have been studied by use of deuterium labelling and tandem mass spectrometry. Loss of ethene from the molecular ion of ethyl phenyl thioether proceeds predominantly by a specific H-shift from the β-position of the ethyl group to the remaining part of the ion. In contrast, deuterium labelling reveals that elimination of propene from the molecular ions of the n-propyl phenyl and n-propyl 2,6-dimethylphenyl thioethers involves three competing reactions: (i) a 1,2-hydride shift assisted cleavage of the bond between the propyl group and the sulfur atom yielding an ion–neutral complex of a thiophenyoxy radical and a secondary propyl carbenium ion, which reacts further by proton transfer prior to dissociation; (ii) a partially reversible 1,5-H shift from the β-position to the 2- or 6-position of the ring; and (iii) a 1,3-H shift from the β-position to the sulfur atom. The preference for transfer of a hydrogen atom from the β-position is particularly pronounce for the reactions of the metastable molecular ions of the n-propyl phenyl and n-propyl 2,6-dimethylphenyl thioethers. This indicates that the critical energies of the processes involving H-shifts are lower than the critical energy for propene loss with intermediate formation of an ion–neutral complex. In addition to ethene elimination, ionized ethyl phenyl thioether expels a HS+· radical. This reaction is preceded by an interchange between the hydrogen atoms at the α-methylene group and the hydrogen atoms at the 2- and 6-positions of the ring as observed also for ionized methyl phenyl thioether.

  我们利用氘标记和串联质谱法研究了从电离乙基和正丙基苯基硫醚中损失烯烃的机理。乙基苯基硫醚分子离子中乙烯的损失主要是通过特定的 H 移位从乙基的 β 位转移到离子的其余部分。相反，氘标记显示，正丙基苯基和正丙基 2,6-二甲基苯基硫醚分子离子中丙烯的消除涉及三个竞争反应：(i) 1,2-氢转移辅助丙基和硫原子之间的键的裂解，产生一个噻吩氧自由基和一个仲丙基硒离子的离子中性复合物，该复合物在解离之前通过质子转移进一步反应；(ii) 部分可逆的 1,5-H 转移，从 β 位转移到环的 2 位或 6 位；以及 (iii) 1,3-H 转移，从 β 位转移到硫原子。在正丙基苯基和正丙基 2,6-二甲基苯基硫醚的逸散分子离子的反应中，从 β 位转移一个氢原子的偏好尤其明显。这表明，涉及氢转移的过程的临界能量低于丙烯损失的临界能量，中间形成离子中性复合物。除了乙烯消除外，电离的乙基苯基硫醚还排出一个 HS+- 自由基。在发生这一反应之前，α-亚甲基上的氢原子与环上 2-和 6-位置上的氢原子发生了互换，这一点在电离的甲基苯基硫醚中也可以观察到。
• Arylboronic Acid Deborylation Deuteration via Synergistic Thiol, Lewis Base, and Photoredox Catalysis
  作者：Jianyang Dong、Mo Yu、Fuyang Yue、Hongjian Song、Yuxiu Liu、Linan Wu、Duanyun Si、Cheng Yang、Guang Yang、Qingmin Wang

  DOI：10.1021/acs.orglett.2c00722

  日期：2022.3.18

  A mild method for the deborylation deuteration of arylboronic acids with D2O, mediated by the synergistic combination of a thiol, a Lewis base, and photoredox catalysis, is reported. This reaction showed a broad substrate scope, excellent deuterium incorporation, and functional group tolerance. Therefore, this method is practical for the site-selective D-labeling of bioactive molecules and drug molecules

  报道了一种由硫醇、路易斯碱和光氧化还原催化的协同组合介导的芳基硼酸与 D 2 O脱硼氘化的温和方法。该反应显示出广泛的底物范围、优异的氘掺入和官能团耐受性。因此，该方法对于生物活性分子和药物分子的位点选择性D标记是实用的。