2,3-dibromo-1-(triisopropylsilyl)pyrrole | 93362-53-9

• 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-dibromo-1-(triisopropylsilyl)pyrrole
• 英文别名: (2,3-Dibromopyrrol-1-yl)-tri(propan-2-yl)silane
• CAS: 93362-53-9
• 化学式: C₁₃H₂₃Br₂NSi
• 分子量: 381.226
• InChiKey: OEYCGELYZJXPIB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.04
• 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

• 作为产物：
  描述：

  三异丙基氯硅烷 在 N-溴代丁二酰亚胺(NBS) 、 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 生成 2,3-dibromo-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

• 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：——
• 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.