1-(triisopropylsilyl)-3,4-diiodopyrrole | 130408-85-4

• 分子结构分类: 有机化合物
• 英文名称: 1-(triisopropylsilyl)-3,4-diiodopyrrole
• 英文别名: 3,4-diiodo-1-(triisopropylsilyl)pyrrole；3,4-diiodo-1-(triisopropylsilyl)-1H-pyrrole；3,4-Diiodo-1-tris(isopropyl)silylpyrrol；(3,4-diiodopyrrol-1-yl)-tri(propan-2-yl)silane
• CAS: 130408-85-4
• 化学式: C₁₃H₂₃I₂NSi
• 分子量: 475.227
• InChiKey: UQGBIWIZBONTNI-UHFFFAOYSA-N

物化性质

• 熔点：
  74-76 °C
• 沸点：
  353.0±27.0 °C(Predicted)
• 密度：
  1.61±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.72
• 重原子数：
  17
• 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：

  1-(triisopropylsilyl)-3,4-diiodopyrrole 在 四(三苯基膦)钯 、 1,1'-双(二苯膦基)二茂铁二氯化钯(II)二氯甲烷复合物 、 sodium carbonate 、 三乙胺 作用下， 以 1,4-二氧六环 、 甲醇 、 水 、 甲苯 为溶剂， 反应 24.0h， 生成 bis-3,4-(7,8-dibenzyloxyquinolin-5-yl)-1-(triisopropylsilyl)pyrrole
  参考文献：
  名称：

  海洋生物碱盐蛋白的全合成

  摘要：

  通过全合成证实了具有强细胞毒性的海洋生物碱盐蛋白（1）的结构，其绝对构型确定为（15 S）。合成遵循我们一个人先前报道的策略，并通过修饰的Baeyer-Villiger和Skraup反应有效制备喹啉7,8-二醇单元。所述ø -苄基保护基团在合成通过转移氢解的不伴随减少喹啉环的最后步骤中除去。该方法可用于合成halitulin类似物。

  DOI：

  10.1016/j.tet.2003.02.005
• 作为产物：
  描述：

  三异丙基氯硅烷 在 mercury(II) diacetate 、 碘 、 sodium hydride 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 生成 1-(triisopropylsilyl)-3,4-diiodopyrrole
  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

• Attempts to Mimic Key Bond-Forming Events Associated with the Proposed Biogenesis of the Pentacyclic Lamellarins
  作者：Lorraine C. Axford、Kate E. Holden、Katrin Hasse、Martin G. Banwell、Wolfgang Steglich、Jörg Wagler、Anthony C. Willis

  DOI：10.1071/ch07402

  日期：——

  The pyrrole-tethered veratroles 16 and 27 each engage in PIFA-induced oxidative cyclization reactions to give compounds 22 and 29, respectively, which incorporate a key tricyclic fragment associated with the title natural products. In contrast, the corresponding catechols 11 and 12 only produce polymeric materials on subjection to analogous reaction conditions. Efforts to study lactone ring formation by the oxidative cyclization of catechol 30 and veratrole 38 have been thwarted by an inability to prepare the former substrate and decomposition of the latter. The reported conversions 44 → 45 and 46 → 47 suggest that a C2-carboxy group attached to the pyrrole ring can ‘direct’ the oxidative cyclization of N-tethered aryl groups. The acquisition of compound 22 by the means described herein provides an adventitious and concise route to the racemic modification of the pyrrolo[2,1-a]isoquinoline alkaloid crispine A (52).

  吡咯系链的藜芦烯 16 和 27 在 PIFA 诱导的氧化环化反应中分别生成化合物 22 和 29，其中包含了与标题天然产物相关的关键三环片段。相比之下，相应的儿茶酚 11 和 12 在类似的反应条件下只能生成聚合材料。由于无法制备儿茶酚 30 和 veratrole 38 的氧化环化反应底物以及后者的分解，研究内酯环形成的努力受挫。据报道，44 → 45 和 46 → 47 的转化过程表明，连接在吡咯环上的 C2-羧基可以 "引导 "N-系芳基的氧化环化。通过本文所述的方法获得化合物 22，为吡咯并[2,1-a]异喹啉生物碱 crisPIne A 的外消旋修饰（52）提供了一条简捷的途径。
• 5-Methyl-1-phenylpyrrolo[3,4-d]borepin: a polarized aromatic molecule
  作者：Yoshikazu Sugihara、Ryuta Miyatake、Ichiro Murata、Akira Imamura

  DOI：10.1039/c39950001249

  日期：——

  Spectroscopic data together with molecular orbital calculations show that 5-methyl-1-phenylpyrrolo[3,4-d]borepin is a polar aromatic system, whose stability confirms our guide for construction of stable heteroaromatic compounds.

  光谱数据结合分子轨道计算表明，5-甲基-1-苯基吡咯并[3,4-d]硼啶是一个极性芳香系统，其稳定性证实了我们构建稳定杂芳香化合物的指导原则。
• Rapid and convergent assembly of the polycyclic framework assigned to the cytotoxic marine alkaloid halitulin
  作者：Martin G. Banwell、Andrew M. Bray、Alison J. Edwards、David J. Wong

  DOI：10.1039/b111401h

  日期：2002.5.23

  Compound 3, representing the tetra-O-methyl ether derivative of structure, 1, assigned to the cytotoxic marine alkaloid halitulin, has been assembled in a convergent manner from the readily available building blocks 5, 6 and 11.

  化合物 3 是结构 1 的四-O-甲基醚衍生物，属于具有细胞毒性的海洋生物碱 halitulin，由现成的结构单元 5、6 和 11 以聚合的方式组装而成。
• Heck reactions of amino acid building blocks: application to the synthesis of pyrrololine analogues
  作者：Philip N. Collier、Ian Patel、Richard J.K. Taylor

  DOI：10.1016/s0040-4039(02)00512-9

  日期：2002.4

  Heck reactions of unsaturated amino acid building blocks are described which allow acess to homo- and bis-homophenylalanine derivatives and to gamma,delta-unsaturated amino acids. Preliminary synthetic studies utilising this chemistry for the preparation of pyrrololine and deoxypyrrololine analogues are also reported. (C) 2002 Elsevier Science Ltd. All rights reserved.
• Electron-Transfer Processes in 3,4-Diferrocenylpyrroles: Insight into a Missing Piece of the Polyferrocenyl-Containing Pyrroles Family
  作者：Wil R. Goetsch、Pavlo V. Solntsev、Casey Van Stappen、Anatolii A. Purchel、Semen V. Dudkin、Victor N. Nemykin

  DOI：10.1021/om400901w

  日期：2014.1.13