N-benzenesulfonyl-2,4-dibromopyrrole | 1229516-64-6

• 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: N-benzenesulfonyl-2,4-dibromopyrrole
• 英文别名: 1-(Benzenesulfonyl)-2,4-dibromopyrrole；1-(benzenesulfonyl)-2,4-dibromopyrrole
• CAS: 1229516-64-6
• 化学式: C₁₀H₇Br₂NO₂S
• 分子量: 365.045
• InChiKey: RECUTMYNHYXCPS-UHFFFAOYSA-N

物化性质

• 熔点：
  87-88 °C(Solv: ethyl ether (60-29-7); pentane (109-66-0))
• 沸点：
  464.4±48.0 °C(Predicted)
• 密度：
  1.89±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  47.4
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  N-benzenesulfonyl-2,4-dibromopyrrole 在 正丁基锂 、 二异丙胺 、 1,2-二碘乙烷 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 3.0h， 以97%的产率得到N-benzenesulfonyl-3-bromo-2-iodopyrrole
  参考文献：
  名称：

  Optional Synthesis of 2- or 5-Substituted 3-Bromopyrroles via Bromine-Lithium Exchange of N-Benzenesulfonyl-2,4-dibromopyrrole

  摘要：

  The regioselective bromine-lithium exchange of N-benzenesulfonyl-2,4-dibromopyrrole (6) with n-BuLi followed by treatment with various electrophiles gave 5-substituted 3-bromopyrroles (5) in excellent yields. In contrast, the sequential treatment of 6 with n-BuLi and diisopropylamine followed by quenching with electrophiles produced regioisomeric 2-substituted 3-bromopyrroles (3) selectively. The latter reaction can be rationalized by the rapid equilibration of the C-5 lithio species (4) to the more stable C-2 lithio species (2) in the presence of diisopropylamine.

  DOI：

  10.3987/com-12-s(n)81
• 作为产物：
  描述：

  1-(苯基磺酰基)吡咯 在 N-溴代丁二酰亚胺(NBS) 、 三氟甲磺酸 作用下， 以 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 25.5h， 生成 N-benzenesulfonyl-2,4-dibromopyrrole
  参考文献：
  名称：

  Optional Synthesis of 2- or 5-Substituted 3-Bromopyrroles via Bromine-Lithium Exchange of N-Benzenesulfonyl-2,4-dibromopyrrole

  摘要：

  The regioselective bromine-lithium exchange of N-benzenesulfonyl-2,4-dibromopyrrole (6) with n-BuLi followed by treatment with various electrophiles gave 5-substituted 3-bromopyrroles (5) in excellent yields. In contrast, the sequential treatment of 6 with n-BuLi and diisopropylamine followed by quenching with electrophiles produced regioisomeric 2-substituted 3-bromopyrroles (3) selectively. The latter reaction can be rationalized by the rapid equilibration of the C-5 lithio species (4) to the more stable C-2 lithio species (2) in the presence of diisopropylamine.

  DOI：

  10.3987/com-12-s(n)81

文献信息

• Regioselective Synthesis of 2,4-Differentially Arylated Pyrroles and Its Application to The Synthesis of Lamellarins
  作者：Masatomo Iwao、Tsutomu Fukuda、Mizuho Anzai

  DOI：10.3987/com-15-s(t)49

  日期：——

  been developed. In the last decade, several strategies for the synthesis of 2,4-differentially arylated pyrroles have been reported. They involve the interesting key reactions such as ring formation from 1,3-diaryl-4-nitrobutan-1-ones, carbanion induced pyrrole synthesis from azirines and ketones, ozonolysis of homoallylic ketones followed by Paal–Knorr condensation, gold-catalyzed reaction with N-tosyl

  通过逐步钯催化的 Suzuki-Miyaura 偶联 N-苯磺酰基-4-溴-2-碘吡咯与不同的芳基硼酸，开发了一种合成 2,4-差异芳基化吡咯的有效方法。该方法已应用于海洋天然产物板层素的新合成。引言 吡咯衍生物广泛存在于具有广泛生物活性的天然产物中。它们也嵌入在一些药剂中。此外，它们还被用作制备具有独特电子和光物理特性的功能材料的宝贵组成部分。因此，已经开发了多种用于从头构建环和对吡咯核进行区域选择性功能化的合成方法。在过去的十年里，已经报道了几种合成 2,4-差异芳基化吡咯的策略。它们涉及有趣的关键反应，例如 1,3-diaryl-4-nitrobutan-1-ones 的成环反应、碳负离子诱导的氮杂环丙烷和酮合成吡咯、高烯丙基酮的臭氧分解以及 Paal-Knorr 缩合、金催化反应N-甲苯磺酰基炔基氮丙啶，铑催化的 N-甲苯磺酰基-1,2,3-三唑与末端炔烃或烯基烷基醚的环化反应，铜
• Regiocontrolled halogen dance of 2,5-dibromopyrroles using equilibrium between dibromopyrrolyllithiums
  作者：Tatsuki Okumi、Atsunori Mori、Kentaro Okano

  DOI：10.1039/d2cc06373e

  日期：——

  A regiocontrolled halogen dance reaction of 2,5-dibromopyrroles is described. An N,N-dimethylsulfamoyl group on the pyrrole nitrogen was especially effective for facilitating interconversion of the resulting 2,3- and 2,4-dibromopyrrolyllithiums, rendering the smooth halogen dance reaction. This method was applicable to the formal synthesis of atorvastatin.

  描述了 2,5-二溴吡咯的区域控制卤素舞反应。吡咯氮上的N , N-二甲基氨磺酰基对于促进所得 2,3- 和 2,4-二溴吡咯基锂的相互转化特别有效，使卤素舞反应顺利进行。该方法适用于阿托伐他汀的形式合成。
• Directed Lithiation of <i>N</i>-Benzenesulfonyl-3-bromopyrrole. Electrophile-Controlled Regioselective Functionalization via Dynamic Equilibrium between C-2 and C-5 Lithio Species
  作者：Tsutomu Fukuda、Takeshi Ohta、Ei-ichi Sudo、Masatomo Iwao

  DOI：10.1021/ol100810c

  日期：2010.6.18

  Directed lithiation of N-benzenesulfonyl-3-bromopyrrole (1) with LDA in THF at -78 degrees C generated C-2 lithio species 3 selectively. Reactions of 3 with reactive electrophiles produced the corresponding 2-functionalized pyrroles 4. On the other hand, quenching with less reactive electrophiles generated the corresponding 5-substituted pyrroles 5. The latter unusual functionalization at C-5 could be rationalized by dynamic equilibrium between C-2 and C-5 lithio species,
• Optional Synthesis of 2- or 5-Substituted 3-Bromopyrroles via Bromine-Lithium Exchange of N-Benzenesulfonyl-2,4-dibromopyrrole
  作者：Masatomo Iwao、Tsutomu Fukuda

  DOI：10.3987/com-12-s(n)81

  日期：——

  The regioselective bromine-lithium exchange of N-benzenesulfonyl-2,4-dibromopyrrole (6) with n-BuLi followed by treatment with various electrophiles gave 5-substituted 3-bromopyrroles (5) in excellent yields. In contrast, the sequential treatment of 6 with n-BuLi and diisopropylamine followed by quenching with electrophiles produced regioisomeric 2-substituted 3-bromopyrroles (3) selectively. The latter reaction can be rationalized by the rapid equilibration of the C-5 lithio species (4) to the more stable C-2 lithio species (2) in the presence of diisopropylamine.