seleno-(2-pyridyl) p-tolueneselenosulfonate | 149419-62-5

• 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: seleno-(2-pyridyl) p-tolueneselenosulfonate
• 英文别名: 2-(4-methylphenyl)sulfonylselanylpyridine
• CAS: 149419-62-5
• 化学式: C₁₂H₁₁NO₂SSe
• 分子量: 312.251
• InChiKey: BHJJIGKPMBLDDB-UHFFFAOYSA-N

物化性质

• 沸点：
  454.2±47.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.11
• 重原子数：
  17.0
• 可旋转键数：
  3.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.08
• 拓扑面积：
  47.03
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  seleno-(2-pyridyl) p-tolueneselenosulfonate 在 偶氮二异丁腈 、 三乙胺 作用下， 以 氯仿 为溶剂， 生成 (E)-2-(2-pyridylseleno)-1-(p-toluenesulfonyl)-2-hexene
  参考文献：
  名称：

  Asymmetric selenoxide elimination leading to chiral allenic sulfones

  摘要：

  Asymmetric oxidation of some aryl vinyl selenides (3) with Sharpless (A-C), modified Sharpless (D) or David oxidants (E-G) resulted in the formation of chiral allenic sulfones 5 of up to 42% enantiomeric excess (ee) via double asymmetric induction, i.e., asymmetric oxidation to selenoxide followed by its asymmetric elimination. The nature of aryl group of the selenides 3 showed a remarkable effect upon the ee of the product: o-nitrophenyl group (a) gave the highest ee, followed by o,p-dinitrophenyl (b), o-(trifluoromethyl)phenyl (e), and o-methoxyphenyl (f) groups, while phenyl (e) and 2-pyridyl (d) groups were not effective at all. The effects of aryl groups were kinetically analyzed by comparing the rate constants of both steps (k1 for oxidation step and k2 for elimination step) which were determined by H-1-NMR analysis of the concentration of 3, the intermediate selenoxides 4, and 5. As a result, it was disclosed that the ratio of these rate constants (k1/k2) Was closely related to the ee of the product; the smaller the ratio is, the larger the ee becomes.

  DOI：

  10.1021/jo00066a023
• 作为产物：
  描述：

  二(2-吡啶基)二硒醚 在 双氧水 作用下， 生成 seleno-(2-pyridyl) p-tolueneselenosulfonate
  参考文献：
  名称：

  Asymmetric selenoxide elimination leading to chiral allenic sulfones

  摘要：

  Asymmetric oxidation of some aryl vinyl selenides (3) with Sharpless (A-C), modified Sharpless (D) or David oxidants (E-G) resulted in the formation of chiral allenic sulfones 5 of up to 42% enantiomeric excess (ee) via double asymmetric induction, i.e., asymmetric oxidation to selenoxide followed by its asymmetric elimination. The nature of aryl group of the selenides 3 showed a remarkable effect upon the ee of the product: o-nitrophenyl group (a) gave the highest ee, followed by o,p-dinitrophenyl (b), o-(trifluoromethyl)phenyl (e), and o-methoxyphenyl (f) groups, while phenyl (e) and 2-pyridyl (d) groups were not effective at all. The effects of aryl groups were kinetically analyzed by comparing the rate constants of both steps (k1 for oxidation step and k2 for elimination step) which were determined by H-1-NMR analysis of the concentration of 3, the intermediate selenoxides 4, and 5. As a result, it was disclosed that the ratio of these rate constants (k1/k2) Was closely related to the ee of the product; the smaller the ratio is, the larger the ee becomes.

  DOI：

  10.1021/jo00066a023

文献信息

• Generation and fate of nondecarboxylating acyloxy radicals derived from the photolysis of acyl derivatives of N-hydroxy-2-thiopyridone
  作者：Derek H.R. Barton、Manlan Ramesh

  DOI：10.1016/s0040-4039(00)94400-9

  日期：1990.1

  The acyl derivatives of 1 with the acyl group linked to aryl, vinyl etc. give on photolysis carboxy radicals. These radicals, by attack on the thiopyridone function, afford thio-peresters which are the real precursors of the anhydrides observed before. The benzoyloxy radical from 2 can be trapped by ethylvinyl ether to give adduct 14 in promising yield.

  具有与芳基，乙烯基等连接的酰基的1的酰基衍生物在光解中产生羧基。这些自由基通过攻击硫代吡啶酮官能团而得到硫代-过酸酯，其是之前观察到的酸酐的真正前体。来自2的苯甲酰氧基可被乙基乙烯基醚捕获，以有希望的产率得到加合物14。
• Coupling of 1-Chloro-<i>N</i>,<i>N</i>-diisopropylphosphanamine-Based Reagents with Alcohols and Thiosulfonates: A Precise Construction of O–P(O)–S Bonds
  作者：Feroze Hussain、Tariq Ahmad Dar、Qazi Naveed Ahmed

  DOI：10.1021/acs.orglett.2c01947

  日期：2022.7.29

  present the first mild, one-step direct synthesis of mixed phosphorothioates through selective generation of O–P(O)–S bonds at rt under additive-free condition. Further, reactions of different model natural products with 1,1-dichloro-N,N-diisopropylphosphanamine helped to present an alternative dimerization strategy. The synthetic utility of the methodology was extended for the synthesis of mixed phosphoroselenoates

  在此，我们提出了第一个温和的一步直接合成混合硫代磷酸酯的方法，该合成方法是在无添加剂条件下在室温下选择性生成 O-P(O)-S 键。此外，不同模型天然产物与 1,1-二氯-N , N-二异丙基膦胺的反应有助于提出另一种二聚化策略。该方法的合成效用也扩展到了混合硒酸磷酸酯的合成。进一步证明了该反应的潜力可用于合成带有两种不同醇的混合硫代磷酸酯。
• Sulfonyl-Promoted Michaelis–Arbuzov-Type Reaction: An Approach to S/Se–P Bonds
  作者：Suhail A. Rather、Mohammad Yaqoob Bhat、Feroze Hussain、Qazi Naveed Ahmed

  DOI：10.1021/acs.joc.1c01681

  日期：2021.10.1