2,3,4-tribromo-1-(triisopropylsilyl)pyrrole | 93362-20-0

• 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: 2,3,4-tribromo-1-(triisopropylsilyl)pyrrole
• 英文别名: Tri(propan-2-yl)-(2,3,4-tribromopyrrol-1-yl)silane
• CAS: 93362-20-0
• 化学式: C₁₃H₂₂Br₃NSi
• 分子量: 460.122
• InChiKey: MRHAEMTZDNZSOM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.8
• 重原子数：
  18
• 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：

  2,3,4-tribromo-1-(triisopropylsilyl)pyrrole 在 正丁基锂 、 水 作用下， 以85%的产率得到N-(三异丙基甲硅烷基)-3,4-二溴吡咯
  参考文献：
  名称：

  通过3-溴-1-（三丙基丙基甲硅烷基）吡咯的卤素-金属交换得到3-硫代吡咯。Verucarin E和其他3取代的吡咯的合成。初步沟通†

  摘要：

  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。

  DOI：

  10.1002/hlca.19840670430
• 作为产物：
  描述：

  1-(三异丙基甲硅烷基)吡咯 在 N-溴代丁二酰亚胺(NBS) 作用下， 以 四氢呋喃 为溶剂， 以91%的产率得到2,3,4-tribromo-1-(triisopropylsilyl)pyrrole
  参考文献：
  名称：

  Convergent syntheses of the pyrrolic marine natural products lamellarin-O, lamellarin-Q, lukianol-A and some more highly oxygenated congeners

  摘要：

  海洋生物碱lamellarin-Q 1、lamellarin-O 2和lukianol-A 3以及它们的更高氧化的同系物22和23，都是通过以Stille、Suzuki或Negishi交叉偶联反应作为关键步骤来合成的。

  DOI：

  10.1039/a606793j

文献信息

• Regioselective Couplings of Dibromopyrrole Esters
  作者：Scott Handy、Yanan Zhang

  DOI：10.1055/s-2006-950305

  日期：2006.11

  The regioselectivity of the Suzuki couplings of several 4,5- and 3,4-dibromopyrrole-2-carboxylate esters has been studied. In general, regioselectivity can be achieved for initial coupling at the more electron-deficient site (C5 and C3, respectively). At the same time, conversions are often modest (40-60%) and attempts to force the reactions to higher conversions often lead to competitive dicoupling.

  研究了几种 4,5- 和 3,4- 二溴吡咯-2-羧酸酯的铃木偶联反应的区域选择性。一般来说，在较缺电子的位点（分别为 C5 和 C3）进行初始偶联时，可以实现区域选择性。与此同时，转化率往往不高（40-60%），试图将反应推向更高的转化率往往会导致竞争性二偶联。
• Red-emissive Polyphenylated BODIPY Derivatives: Effect of Peripheral Phenyl Groups on the Photophysical and Electrochemical Properties
  作者：Atsushi Wakamiya、Naoya Sugita、Shigehiro Yamaguchi

  DOI：10.1246/cl.2008.1094

  日期：2008.10.5

  A series of red-emissive BODIPY derivatives 2–4 having five to seven phenyl groups on their periphery were synthesized, and their photophysical and electrochemical properties were investigated. While the 8-phenyl-substituted derivatives only have moderate fluorescence quantum yields in solution, they can show intense red fluorescence in the PMMA films. The peripheral phenyl groups also affect the redox reversibility in cyclic voltammetry.

  研究人员合成了一系列外围具有 5 到 7 个苯基的红色发射性 BODIPY 衍生物 2-4，并研究了它们的光物理和电化学性质。虽然 8 苯基取代的衍生物在溶液中只有中等的荧光量子产率，但在 PMMA 薄膜中却能显示出强烈的红色荧光。外围苯基基团还会影响循环伏安法中的氧化还原性。
• Modular Total Synthesis of the 5/5-Spirocyclic Spiroindimicins
  作者：Ankush Banerjee、Tiffany A. Brisco、Zhen Zhang、Alexander A. Busse、Krissty Sumida、Myles W. Smith

  DOI：10.1021/acs.orglett.3c03131

  日期：2023.12.1

  Total syntheses of the 5/5-spirocyclic indoline alkaloids (±)-spiroindimicins B, C, D, E, F, and G have been achieved via a modular approach. Our route features direct coupling of halogenated pyrrolemetal and isatin partners, Suzuki coupling to append the indole unit, Lewis acid-mediated spirocyclization, and divergent functionalization to give various family members. These syntheses are concise (six

  通过模块化方法实现了 5/5-螺环二氢吲哚生物碱 (±)-spiroindimicins B、C、D、E、F 和 G 的全合成。我们的路线的特点是卤化吡咯金属和靛红伴侣的直接偶联、铃木偶联以附加吲哚单元、路易斯酸介导的螺环化以及不同的官能化以产生各种家族成员。这些合成很简洁（来自商业材料的六到七个步骤）并且非常适合模拟合成。
• Solid-phase synthesis of lamellarins Q and O
  作者：Marta Marfil、Fernando Albericio、Mercedes Álvarez

  DOI：10.1016/j.tet.2004.05.110

  日期：2004.9

  An efficient solid phase synthesis of the pyrrole-based alkaloids lamellarins Q and O using Merrifield resin and N-protected methyl 3,4-dibromopyrrole-2-carboxylate as a scaffold is described. (C) 2004 Elsevier Ltd. All rights reserved.
• N-(Triisopropylsilyl)pyrrole. A progenitor "par excellence" of 3-substituted pyrroles
  作者：Brian L. Bray、Peter H. Mathies、Reto Naef、Dennis R. Solas、Thomas T. Tidwell、Dean R. Artis、Joseph M. Muchowski

  DOI：10.1021/jo00313a019

  日期：1990.12

  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.