{2-[2-bromo-6-(3-methylbut-2-enyl)phenylsulfanyl]ethyl}trimethylsilane | 532412-74-1

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: {2-[2-bromo-6-(3-methylbut-2-enyl)phenylsulfanyl]ethyl}trimethylsilane
• 英文别名: 1-Bromo-2-[2-(trimethylsilyl)ethyl]thio-3-(3-methylbut-2-en-1-yl)benzene；2-[2-bromo-6-(3-methylbut-2-enyl)phenyl]sulfanylethyl-trimethylsilane
• CAS: 532412-74-1
• 化学式: C₁₆H₂₅BrSSi
• 分子量: 357.43
• InChiKey: HAADEIPOTWBRPD-UHFFFAOYSA-N

物化性质

• 沸点：
  378.7±42.0 °C(Predicted)
• 密度：
  1.15±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.39
• 重原子数：
  19
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  25.3
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  {2-[2-bromo-6-(3-methylbut-2-enyl)phenylsulfanyl]ethyl}trimethylsilane 在 正丁基锂 、 草酰氯 、 三乙胺 、 N,N-二甲基甲酰胺 作用下， 以 四氢呋喃 、 正己烷 、 氯仿 、 苯 为溶剂， 反应 2.25h， 生成 3-(3-methylbut-2-enyl)-2-[2-(trimethylsilanyl)ethylsulfanyl]thiobenzoic acid S-[2-(trimethylsilanyl)ethyl]ester
  参考文献：
  名称：

  Small Molecules That Mimic the Thiol-Triggered Alkylating Properties Seen in the Natural Product Leinamycin

  摘要：

  Reaction of the antitumor agent leinamycin with cellular thiols results in conversion of the natural product to a DNA-alkylating episulfonium alkylating agent via an intriguing sequence of chemical reactions. To establish whether the chemistry first seen in leinamycin represents a general motif that can function in various molecular frameworks, construction of greatly simplified analogues containing only the "core" funcional groups anticipated to be necessary for thiol-triggered generation of an alkylating agent was undertaken. For this purpose, the "stripped-down" leinamycin analogue 7-(3-methyl-but-2-enyl)-1-oxo-1H-lambda4-benzo[1,2]dithiol-3-one (4) was synthesized. Treatment of 4 with thiol under several different conditions results in efficient conversion of the compound to cyclized 2,3-dihydro-benzo[b]thiophene-7-carboxylic acid products (13) that are envisioned to arise from Markovnikov addition of solvent to an intermediate episulfonium ion (14). Thus, the relatively simple molecule 4 is able to mimic the thiol-triggered alkylating properties displayed by the natural product leinamycin. This work helps define why the core functional groups required thiol-accelerated generation of an alkylating intermediate from leinamycin and indicates that substantially altered analogues of the natural product may retain alkylating properties. In a broader context, the results provide evidence that the unique cascade of chemical reactions first seen in the context of leinamycin represents a general motif that can operate in a variety of molecular frameworks.

  DOI：

  10.1021/ja029169y
• 作为产物：
  描述：

  2-(三甲基硅烷)乙硫醇 在 正丁基锂 、 sodium hydride 作用下， 以 四氢呋喃 、 正己烷 、 二甲基亚砜 为溶剂， 反应 11.58h， 生成 {2-[2-bromo-6-(3-methylbut-2-enyl)phenylsulfanyl]ethyl}trimethylsilane
  参考文献：
  名称：

  Small Molecules That Mimic the Thiol-Triggered Alkylating Properties Seen in the Natural Product Leinamycin

  摘要：

  Reaction of the antitumor agent leinamycin with cellular thiols results in conversion of the natural product to a DNA-alkylating episulfonium alkylating agent via an intriguing sequence of chemical reactions. To establish whether the chemistry first seen in leinamycin represents a general motif that can function in various molecular frameworks, construction of greatly simplified analogues containing only the "core" funcional groups anticipated to be necessary for thiol-triggered generation of an alkylating agent was undertaken. For this purpose, the "stripped-down" leinamycin analogue 7-(3-methyl-but-2-enyl)-1-oxo-1H-lambda4-benzo[1,2]dithiol-3-one (4) was synthesized. Treatment of 4 with thiol under several different conditions results in efficient conversion of the compound to cyclized 2,3-dihydro-benzo[b]thiophene-7-carboxylic acid products (13) that are envisioned to arise from Markovnikov addition of solvent to an intermediate episulfonium ion (14). Thus, the relatively simple molecule 4 is able to mimic the thiol-triggered alkylating properties displayed by the natural product leinamycin. This work helps define why the core functional groups required thiol-accelerated generation of an alkylating intermediate from leinamycin and indicates that substantially altered analogues of the natural product may retain alkylating properties. In a broader context, the results provide evidence that the unique cascade of chemical reactions first seen in the context of leinamycin represents a general motif that can operate in a variety of molecular frameworks.

  DOI：

  10.1021/ja029169y

文献信息

• Small Molecules That Mimic the Thiol-Triggered Alkylating Properties Seen in the Natural Product Leinamycin
  作者：Tonika Chatterji、Murat Kizil、Kripa Keerthi、Goutam Chowdhury、Tomás Pospísil、Kent S. Gates

  DOI：10.1021/ja029169y

  日期：2003.4.1

  Reaction of the antitumor agent leinamycin with cellular thiols results in conversion of the natural product to a DNA-alkylating episulfonium alkylating agent via an intriguing sequence of chemical reactions. To establish whether the chemistry first seen in leinamycin represents a general motif that can function in various molecular frameworks, construction of greatly simplified analogues containing only the "core" funcional groups anticipated to be necessary for thiol-triggered generation of an alkylating agent was undertaken. For this purpose, the "stripped-down" leinamycin analogue 7-(3-methyl-but-2-enyl)-1-oxo-1H-lambda4-benzo[1,2]dithiol-3-one (4) was synthesized. Treatment of 4 with thiol under several different conditions results in efficient conversion of the compound to cyclized 2,3-dihydro-benzo[b]thiophene-7-carboxylic acid products (13) that are envisioned to arise from Markovnikov addition of solvent to an intermediate episulfonium ion (14). Thus, the relatively simple molecule 4 is able to mimic the thiol-triggered alkylating properties displayed by the natural product leinamycin. This work helps define why the core functional groups required thiol-accelerated generation of an alkylating intermediate from leinamycin and indicates that substantially altered analogues of the natural product may retain alkylating properties. In a broader context, the results provide evidence that the unique cascade of chemical reactions first seen in the context of leinamycin represents a general motif that can operate in a variety of molecular frameworks.