3-(trifluoroacetyl)-1-(triisopropylsilyl)pyrrole | 130408-88-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3-(trifluoroacetyl)-1-(triisopropylsilyl)pyrrole
• 英文别名: 2,2,2-trifluoro-1-{1-[tris(propan-2-yl)silyl]-1H-pyrrol-3-yl}ethan-1-one；2,2,2-trifluoro-1-[1-tri(propan-2-yl)silylpyrrol-3-yl]ethanone
• CAS: 130408-88-7
• 化学式: C₁₅H₂₄F₃NOSi
• mdl: MFCD22378615
• 分子量: 319.442
• InChiKey: NDWKCTCUEMITEU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  21
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.666
• 拓扑面积：
  22
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  3-(trifluoroacetyl)-1-(triisopropylsilyl)pyrrole 在 四丁基氟化铵 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 0.17h， 以67%的产率得到2,2,2-三氟-1-(1H-吡咯-3-基)-1-乙酮
  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
• 作为产物：
  描述：

  三异丙基氯硅烷 在 吡啶 、 sodium hydride 作用下， 以 二氯甲烷 为溶剂， 反应 5.0h， 生成 3-(trifluoroacetyl)-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

• 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.