(S)-1-((1S,2R,4S)-Bicyclo[2.2.1]hept-5-ene-2-carbonyl)-pyrrolidine-2-carboxylic acid methyl ester | 136030-81-4

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: (S)-1-((1S,2R,4S)-Bicyclo[2.2.1]hept-5-ene-2-carbonyl)-pyrrolidine-2-carboxylic acid methyl ester
• 英文别名: methyl (2S)-1-[(1S,2R,4S)-bicyclo[2.2.1]hept-5-ene-2-carbonyl]pyrrolidine-2-carboxylate
• CAS: 136030-81-4
• 化学式: C₁₄H₁₉NO₃
• 分子量: 249.31
• InChiKey: KCHQWALIASWGCQ-QCNOEVLYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  46.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  环戊二烯 、 N-acryloyl-L-proline methyl ester 在 三氯化铝 作用下， 生成 (S)-1-((1S,2R,4S)-Bicyclo[2.2.1]hept-5-ene-2-carbonyl)-pyrrolidine-2-carboxylic acid methyl ester 、 N-<(1R,2R,4R)-bicyclo<2.2.1>hept-5-en-2-ylcarbonyl>-(S)-proline methyl ester 、 N-<(1S,2S,4S)-bicyclo<2.2.1>hept-5-en-2-ylcarbonyl>-(S)-proline methyl ester 、 (S)-1-((1R,2S,4R)-Bicyclo[2.2.1]hept-5-ene-2-carbonyl)-pyrrolidine-2-carboxylic acid methyl ester
  参考文献：
  名称：

  Models for the use of .alpha.-amino acids as chiral auxiliaries in asymmetric Diels-Alder reactions

  摘要：

  Three different models, depending on the Lewis acid used as a catalyst and the alpha-amino acid used as a chiral auxiliary, account for the diastereofacial selectivity obtained in reactions of cyclopentadiene with N-acryloyl derivatives of L-proline, L-phenylalanine, L-alanine, and N-methyl-L-alanine esters. For alpha-amino acids without an NH group and aluminum catalysts, a reactive conformer with antiplanar enoate conformation similar to those postulated for acrylates with only one center capable of coordination is proposed. These dienophiles form a chelate complex, where the acryloyl moiety is in syn conformation, with TiCl4. For alpha-amino acids with an NH group, a reactive intermediate with an antiplanar disposition in the acryloyl moiety and the conformation of the amino ester fixed by an intramolecular hydrogen bond accounts for the results with both kinds of catalyst. These models seem to have general application for the use of alpha-amino acids as chiral auxiliaries in asymmetric Diels-Alder reactions.

  DOI：

  10.1021/jo00023a020

文献信息

• Models for the use of .alpha.-amino acids as chiral auxiliaries in asymmetric Diels-Alder reactions
  作者：Maria P. Bueno、Carlos A. Cativiela、Jose A. Mayoral、Alberto Avenoza

  DOI：10.1021/jo00023a020

  日期：1991.11

  Three different models, depending on the Lewis acid used as a catalyst and the alpha-amino acid used as a chiral auxiliary, account for the diastereofacial selectivity obtained in reactions of cyclopentadiene with N-acryloyl derivatives of L-proline, L-phenylalanine, L-alanine, and N-methyl-L-alanine esters. For alpha-amino acids without an NH group and aluminum catalysts, a reactive conformer with antiplanar enoate conformation similar to those postulated for acrylates with only one center capable of coordination is proposed. These dienophiles form a chelate complex, where the acryloyl moiety is in syn conformation, with TiCl4. For alpha-amino acids with an NH group, a reactive intermediate with an antiplanar disposition in the acryloyl moiety and the conformation of the amino ester fixed by an intramolecular hydrogen bond accounts for the results with both kinds of catalyst. These models seem to have general application for the use of alpha-amino acids as chiral auxiliaries in asymmetric Diels-Alder reactions.