N-(2-methylbenzoyl)-L-proline

• 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: N-(2-methylbenzoyl)-L-proline
• 英文别名: N-(2-methylbenzoyl)-(s)-proline；(2S)-1-(2-methylbenzoyl)pyrrolidine-2-carboxylic acid
• 化学式: C₁₃H₁₅NO₃
• mdl: MFCD15732055
• 分子量: 233.267
• InChiKey: XDXPQZCLBZNWBV-NSHDSACASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  57.6
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  甲醇 、 N-(2-methylbenzoyl)-L-proline 在 氯化亚砜 作用下， 反应 1.0h， 以80%的产率得到N-(2-甲基苯甲酰基)-(S)-脯氨酸甲酯
  参考文献：
  名称：

  负载金属催化剂上取代芳烃的非对映选择性加氢

  摘要：

  The purpose of this work was to hydrogenate disubstituted aromatic compounds on supported metal catalysts to produce enantiomers of the corresponding cyclohexane derivatives using a diastereoselective approach, i.e., associating the organic substrates with chiral auxiliaries. The diastereoselective catalytic hydrogenation of N-(2-methylbenzoyl)-(S)-proline methyl ester was performed on carbon-supported metal catalysts, optionally modified by the adsorption of EDCA (ethyldicyclohexylamine). The formation of cis-diastereoisomers predominated and a cyclohexenic compound was formed transiently After cleavage of the proline ester auxiliary, optically active 2-methylcyclohexane carboxylic acids were obtained. The influence on reaction kinetics and diastereoselectivity of various factors were investigated on Rh/C catalysts; these factors were pressure, substrate concentration, particle size, and thermal pretreatments of the rhodium catalysts modified with an amine. The reaction rate and the diastereoisomeric excess were found to be very sensitive to these parameters as well as to the presence of water on the catalyst. The importance of the nature of the metal (Rh, Ru, Pt, Pd) was clearly demonstrated. Pt and Pd showed very low activity. Without addition of amine, unmodified rhodium catalysts were nonselective as long as the aromatic substrate was present, whereas the ruthenium catalysts produced moderate selectivity. In the latter case, the carbonyl and carboxyl groups of the molecule could interact with the surface, thus determining which face of the aromatic ring would be preferentially adsorbed. Then, because of the consecutive hydrogenation of the cyclohexenic compound, diastereoselective excesses (d.e.) of 17 and 32%, respectively, were observed in favor of the (1R,2S,2'S) isomer. In the presence of an achiral amine (e.g., EDCA) on rhodium catalysts, d.e. attaining ca. 50% were measured in favor of the (1S,2R,2'S) isomer. No inversion of configuration was observed with modified ruthenium, probably because the aromatic substrate is more strongly bonded to the surface than in the case of rhodium and thus displaces the amine. In contrast, the aromatic substrate is weakly bonded to platinum and palladium compared to the EDCA molecules which block the surface, In the absence of amine, the weaker adsorption of the aromatic substrate is responsible for the formation of irans products. (C) 1997 Academic Press.

  DOI：

  10.1006/jcat.1997.1722
• 作为产物：
  描述：

  对甲苯甲酸 在 草酰氯 、 N,N-二甲基甲酰胺 、 sodium hydroxide 作用下， 以 四氢呋喃 、 水 、 甲苯 为溶剂， 反应 4.0h， 生成 N-(2-methylbenzoyl)-L-proline
  参考文献：
  名称：

  保留N-（2-苯基）苯甲酰基的5元脂环族α-氨基酸在光诱导丙烯腈脱羧分子间自由基中的手性

  摘要：

  在温和的有机光氧化还原催化条件下，将带有（2-苯基）苯甲酰基保护基的5元脂环族α-氨基酸的光诱导脱羧自由基加成到丙烯腈上，通过手性记忆（MOC），γ-氨基酸衍生物具有高度的手性保留能力战略。在光诱导的脱羧中手性的保留强烈依赖于脂环族α-氨基酸和烯烃的结构。据我们所知，这是使用MOC策略将烯烃脱羧分子间自由基加成至烯烃并在自由基生成位置保留手性的第一个例子。

  DOI：

  10.1016/j.tet.2019.130493

文献信息

• Retention of chirality of 5-membered alicyclic α-amino acids bearing N-(2-phenyl)benzoyl group in photoinduced decarboxylative intermolecular radical addition to acrylonitrile
  作者：Yui Ozaki、Tomoaki Yamada、Taisei Mizuno、Kazuyuki Osaka、Mugen Yamawaki、Hajime Maeda、Toshio Morita、Yasuharu Yoshimi

  DOI：10.1016/j.tet.2019.130493

  日期：2019.9

  5-membered alicyclic α-amino acids bearing a (2-phenyl)benzoyl protective group to acrylonitrile under mild organic photoredox catalysis conditions furnished γ-amino acid derivatives with high retention of chirality via the memory of chirality (MOC) strategy. The retention of chirality in the photoinduced decarboxylation was strongly dependent on the structure of the alicyclic α-amino acids and alkenes. To

  在温和的有机光氧化还原催化条件下，将带有（2-苯基）苯甲酰基保护基的5元脂环族α-氨基酸的光诱导脱羧自由基加成到丙烯腈上，通过手性记忆（MOC），γ-氨基酸衍生物具有高度的手性保留能力战略。在光诱导的脱羧中手性的保留强烈依赖于脂环族α-氨基酸和烯烃的结构。据我们所知，这是使用MOC策略将烯烃脱羧分子间自由基加成至烯烃并在自由基生成位置保留手性的第一个例子。
• Diastereoselective Hydrogenation of Substituted Aromatics on Supported Metal Catalysts
  作者：Michèle Besson、Bernard Blanc、Muriel Champelet、Pierre Gallezot、Kamel Nasar、Catherine Pinel

  DOI：10.1006/jcat.1997.1722

  日期：1997.1

  The purpose of this work was to hydrogenate disubstituted aromatic compounds on supported metal catalysts to produce enantiomers of the corresponding cyclohexane derivatives using a diastereoselective approach, i.e., associating the organic substrates with chiral auxiliaries. The diastereoselective catalytic hydrogenation of N-(2-methylbenzoyl)-(S)-proline methyl ester was performed on carbon-supported metal catalysts, optionally modified by the adsorption of EDCA (ethyldicyclohexylamine). The formation of cis-diastereoisomers predominated and a cyclohexenic compound was formed transiently After cleavage of the proline ester auxiliary, optically active 2-methylcyclohexane carboxylic acids were obtained. The influence on reaction kinetics and diastereoselectivity of various factors were investigated on Rh/C catalysts; these factors were pressure, substrate concentration, particle size, and thermal pretreatments of the rhodium catalysts modified with an amine. The reaction rate and the diastereoisomeric excess were found to be very sensitive to these parameters as well as to the presence of water on the catalyst. The importance of the nature of the metal (Rh, Ru, Pt, Pd) was clearly demonstrated. Pt and Pd showed very low activity. Without addition of amine, unmodified rhodium catalysts were nonselective as long as the aromatic substrate was present, whereas the ruthenium catalysts produced moderate selectivity. In the latter case, the carbonyl and carboxyl groups of the molecule could interact with the surface, thus determining which face of the aromatic ring would be preferentially adsorbed. Then, because of the consecutive hydrogenation of the cyclohexenic compound, diastereoselective excesses (d.e.) of 17 and 32%, respectively, were observed in favor of the (1R,2S,2'S) isomer. In the presence of an achiral amine (e.g., EDCA) on rhodium catalysts, d.e. attaining ca. 50% were measured in favor of the (1S,2R,2'S) isomer. No inversion of configuration was observed with modified ruthenium, probably because the aromatic substrate is more strongly bonded to the surface than in the case of rhodium and thus displaces the amine. In contrast, the aromatic substrate is weakly bonded to platinum and palladium compared to the EDCA molecules which block the surface, In the absence of amine, the weaker adsorption of the aromatic substrate is responsible for the formation of irans products. (C) 1997 Academic Press.