methyl 5-methyl-2-phenyl-4-phenylacetyl-1H-pyrrole-3-carboxylate | 1371568-69-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯
• 英文名称: methyl 5-methyl-2-phenyl-4-phenylacetyl-1H-pyrrole-3-carboxylate
• 英文别名: methyl 5-methyl-2-phenyl-4-(2-phenylacetyl)-1H-pyrrole-3-carboxylate
• CAS: 1371568-69-2
• 化学式: C₂₁H₁₉NO₃
• 分子量: 333.387
• InChiKey: ZUSJKPZDESETQH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  25
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  59.2
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  苯乙炔 在 溴乙烷 、 magnesium 、 potassium iodide 、 palladium(II) iodide 作用下， 以 四氢呋喃 为溶剂， 反应 17.25h， 生成 methyl 5-methyl-2-phenyl-4-phenylacetyl-1H-pyrrole-3-carboxylate
  参考文献：
  名称：

  A Palladium Iodide-Catalyzed Carbonylative Approach to Functionalized Pyrrole Derivatives

  摘要：

  A novel and convenient approach to functionalized pyrroles is presented, based on Pd-catalyzed oxidative heterocyclization-alkoxycarbonylation of readily available N-Boc-1-amino-3-yn-2-ols. Reactions were carried out in alcoholic solvents at 80-100 degrees C and under 20 atm (at 25 degrees C) of a 4:1 mixture of CO air, in the presence of the PdI2-KI catalytic system (2-5 mol % of PdI2, KI/PdI2, molar ratio = 10). In the case of N-Boc-1-amino-3-yn-2-ols 3, bearing alkyl or aryl substituents, the carbonylation reaction led to a mixture of Boc-protected and N-unsubstituted pyrrole-3-carboxylic esters 4 and 5, respectively. This mixture could be conveniently and quantitatively converted into deprotected pyrrole-3-carboxylic esters 5 by a simple basic treatment. In the case of diastereomeric (3RS,4RS)- and (3RS,4SR)-N-Boc-3-amino-2-methyldec-5-yn-4-ol (syn-3f and anti-3f, respectively, whose relative configuration was determined by X-ray crystallographic analysis), no particular difference was observed in the reactivity of the two diastereomers between them and with respect to the diastereomeric mixture (3S,4S) + (3S,4R). Interestingly, N-Boc-2-alkynyl-1-amino-3-yn-2-ols 6, bearing an additional alkynyl substituent alpha to the hydroxyl group, spontaneously underwent N-deprotection under the reaction conditions and regioselective water addition to the alkynyl group at C-3 of the corresponding pyrrole-3-carboxylic ester derivative, thus directly affording highly functionalized pyrrole derivatives 7 in one step. In a similar manner, a novel functionalized dihydropyrrolizine derivative 9 was directly synthesized starting from (S)-7-(pyrrolidin-2-yl)trideca-5,8-diyn-7-ol 8.

  DOI：

  10.1021/jo300365n

文献信息

• A Palladium Iodide-Catalyzed Carbonylative Approach to Functionalized Pyrrole Derivatives
  作者：Bartolo Gabriele、Lucia Veltri、Raffaella Mancuso、Giuseppe Salerno、Sabino Maggi、Brunella Maria Aresta

  DOI：10.1021/jo300365n

  日期：2012.4.20

  A novel and convenient approach to functionalized pyrroles is presented, based on Pd-catalyzed oxidative heterocyclization-alkoxycarbonylation of readily available N-Boc-1-amino-3-yn-2-ols. Reactions were carried out in alcoholic solvents at 80-100 degrees C and under 20 atm (at 25 degrees C) of a 4:1 mixture of CO air, in the presence of the PdI2-KI catalytic system (2-5 mol % of PdI2, KI/PdI2, molar ratio = 10). In the case of N-Boc-1-amino-3-yn-2-ols 3, bearing alkyl or aryl substituents, the carbonylation reaction led to a mixture of Boc-protected and N-unsubstituted pyrrole-3-carboxylic esters 4 and 5, respectively. This mixture could be conveniently and quantitatively converted into deprotected pyrrole-3-carboxylic esters 5 by a simple basic treatment. In the case of diastereomeric (3RS,4RS)- and (3RS,4SR)-N-Boc-3-amino-2-methyldec-5-yn-4-ol (syn-3f and anti-3f, respectively, whose relative configuration was determined by X-ray crystallographic analysis), no particular difference was observed in the reactivity of the two diastereomers between them and with respect to the diastereomeric mixture (3S,4S) + (3S,4R). Interestingly, N-Boc-2-alkynyl-1-amino-3-yn-2-ols 6, bearing an additional alkynyl substituent alpha to the hydroxyl group, spontaneously underwent N-deprotection under the reaction conditions and regioselective water addition to the alkynyl group at C-3 of the corresponding pyrrole-3-carboxylic ester derivative, thus directly affording highly functionalized pyrrole derivatives 7 in one step. In a similar manner, a novel functionalized dihydropyrrolizine derivative 9 was directly synthesized starting from (S)-7-(pyrrolidin-2-yl)trideca-5,8-diyn-7-ol 8.