2-bromo-1-(triisopropylsilyl)pyrrole | 130408-79-6

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: 2-bromo-1-(triisopropylsilyl)pyrrole
• 英文别名: 2-Bromo-1-[tris(1-methylethyl)silyl]-1H-pyrrole；(2-bromopyrrol-1-yl)-tri(propan-2-yl)silane
• CAS: 130408-79-6
• 化学式: C₁₃H₂₄BrNSi
• 分子量: 302.33
• InChiKey: DMPLNWVCJMPUHZ-UHFFFAOYSA-N

物化性质

• 沸点：
  281.1±13.0 °C(Predicted)
• 密度：
  1.11±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.27
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.69
• 拓扑面积：
  4.9
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  2-bromo-1-(triisopropylsilyl)pyrrole 在 正丁基锂 、 dimethyl-(4-nitro-buta-1,3-dienyl)-amine 作用下， 以 四氢呋喃 、 正戊烷 为溶剂， 以73.4%的产率得到1-(三异丙基甲硅烷基)吡咯
  参考文献：
  名称：

  Condensation Reactions of a Nitrodienamine with Organocopper and Alkyllithium Reagents Prepared from Pyrrole Derivatives

  摘要：

  Condensation reactions of a nitrodienamine (1) with Grignard, organocopper and alkyllithium reagents prepared from pyrrole derivatives were investigated.

  DOI：

  10.3987/com-00-8859
• 作为产物：
  描述：

  吡咯 、 三异丙基氯硅烷 生成 2-bromo-1-(triisopropylsilyl)pyrrole
  参考文献：
  名称：

  N-(Triisopropylsilyl)pyrrole. A progenitor "par excellence" of 3-substituted pyrroles

  摘要：

  A very effective strategy has been devised for the synthesis of 3-substituted pyrroles based on the use of the triisopropylsilyl (TIPS) moiety as a sterically demanding nitrogen substituent to obstruct the attack of electrophilic reagents at the alpha-positions. 1-(Triisopropylsilyl)pyrrole (1) undergoes highly preferential kinetic electrophilic substitution at the beta-position with a variety of electrophiles (Br+, I+, NO2+, RCO+, etc.) and fluoride ion induced desilylation of the products provides the corresponding 3-substituted pyrroles in good overall yields. Competitive trifluoroacetylation experiments demonstrate that substitution of TIPS-pyrrole at the alpha-positions is decelerated by a factor of > 10(4), vs pyrrole at the same sites, without affecting reactivity at the beta-positions. 1-(Triisopropylsilyl)-3-bromopyrrole (2) is readily converted into the 3-lithio compound 44 by bromine-lithium interchange with alkyllithium reagents. This previously unavailable, formal equivalent of 3-lithiopyrrole is itself an excellent source of a wide range of beta-substituted pyrroles, many of which would not be directly preparable from 1. TIPS-pyrrole can be 3,4-dihalogenated and these compounds undergo sequential halogen-metal interchange trapping reactions. This process is exemplified by an efficient, three-step synthesis of the antibiotic verrucarin E (63) from the dibromo compound 5.

  DOI：

  10.1021/jo00313a019

文献信息

• Crown-Tetrathiafulvalenes Attached to a Pyrrole or an EDOT Unit: Synthesis, Electropolymerization and Recognition Properties
  作者：Gaëlle Trippé、Franck Le Derf、Joël Lyskawa、Miloud Mazari、Jean Roncali、Alain Gorgues、Eric Levillain、Marc Sallé

  DOI：10.1002/chem.200400303

  日期：2004.12.17

  electroactive receptor has been covalently linked to electropolymerizable pyrrole or 3,4-ethylenedioxythiophene monomers. The synthetic route to the monofonctionalized tetrathiafulvalene (TTF) ligand has been optimized. Two derivatives of pyrrole (N- and 3-substituted) were synthesized. The various substituted monomers have been electropolymerized to produce polypyrrole (PP) and poly(ethylenedioxothiophene) (PEDOT)

  冠-四硫富瓦烯冠状电活性受体已与可电聚合的吡咯或3,4-乙撑二氧噻吩单体共价连接。单官能化四硫富瓦烯（TTF）配体的合成路线已得到优化。合成了吡咯的两种衍生物（N-和3-取代的）。各种取代的单体已被电聚合，以产生带有电活性TTF部分的聚吡咯（PP）和聚（乙烯二氧代噻吩）（PEDOT）薄膜。聚合物膜的电活性可以通过TTF单元明确定义的两步氧化还原行为来有效控制。在PEDOT的情况下，已使用了一种替代的聚合后衍生化策略，包括在先前生长的PEDOT骨架上接枝冠状-TTF配体。尽管化学衍生化是在异质条件下实现的，但在整个薄膜中，这种策略被证明是特别有效的。这些电极构成了导电聚合物基修饰电极的第一个示例，该电极结合了TTF电化学探针，能够与客体离子（例如Ba2 +）相互作用。通过循环伏安法分析了这些各种电极的阳离子识别特性，并研究了它们在水中的电活性以及再生能力。
• β-substituted pyrroles via electrophilic substitution of n-triisopropylsilylpyrrole.
  作者：Joseph M Muchowski、Dennis R Solas

  DOI：10.1016/s0040-4039(00)86011-6

  日期：1983.1

  N-Triisopropylsilylpyrrole undergoes predominant or exclusive kinetic electrophilic substiution at C-3, and the compounds obtained thereby, upon desilylation with tetra--butylammonium fluoride, give 3-substituted pyrroles in good overall yields.

  N-三异丙基甲硅烷基吡咯在C-3处经受主要或排他的动力学亲电取代，并且由此获得的化合物在与四丁基氟化铵进行甲硅烷基化后，以良好的总收率得到3-取代的吡咯。
• 3-Lithiopyrroles by Halogen-Metal Interchange of 3-Bromo-1-(triissopropylsilyl)pyrroles. Synthesis of Verucarin E and Other 3-Substituted Pyrroles. Preliminary Communication
  作者：Joseph M. Muchowski、Reto Naef

  DOI：10.1002/hlca.19840670430

  日期：1984.6.20

  3-Lithio-1-(trimethylsilyl)pyrrole (7, Schem 2), obtained by halogen-metal interchange from the 3-bromo compound 2, reacted with various electrophilic reagents to provide products, which on fluoride ion desilylation, gave 3-substituted pyrroles in good overall yields. One such pyrrole 13 (Schem 3), was converted into 2-formyl-3-octadeclpyrrole (14), reputed to be a metabolite of the marine sponge Oscarella

  由3-溴化合物2通过卤素-金属交换制得的3-Lithio-1-（三甲基甲硅烷基）吡咯（7，Schem 2）与各种亲电子试剂反应生成产物，该产物经氟离子去甲硅烷基化后得到3-取代的吡咯具有良好的总收率。一种这样的吡咯13（Schem 3）被转化为2-甲酰基-3-十八烷基吡咯（14），据称是海洋海绵小叶Oscarella lobularis的代谢产物。
• BRAY, BRIAN L.;MATHIES, PETER H.;NAEF, RETO;SOLAS, DENNIS R.;TIDWELL, THO+, J. ORG. CHEM., 55,(1990) N6, C. 6317-6328
  作者：BRAY, BRIAN L.、MATHIES, PETER H.、NAEF, RETO、SOLAS, DENNIS R.、TIDWELL, THO+

  DOI：——

  日期：——
• Condensation Reactions of a Nitrodienamine with Organocopper and Alkyllithium Reagents Prepared from Pyrrole Derivatives
  作者：Takeshi Koike、Yoshifumi Shinohara、Takeshi Nishimura、Masanori Hagiwara、Seisho Tobinaga、Naoki Takeuchi

  DOI：10.3987/com-00-8859

  日期：——

  Condensation reactions of a nitrodienamine (1) with Grignard, organocopper and alkyllithium reagents prepared from pyrrole derivatives were investigated.