N-acetyl-2'-methyl-L-phenylalanine methyl ester | 889863-31-4

• 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: N-acetyl-2'-methyl-L-phenylalanine methyl ester
• 英文别名: (S)-methyl 2-acetamido-3-(o-tolyl)propanoate；methyl (2S)-2-acetamido-3-(2-methylphenyl)propanoate
• CAS: 889863-31-4
• 化学式: C₁₃H₁₇NO₃
• 分子量: 235.283
• InChiKey: AYPQMSIXFSQKKC-LBPRGKRZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  17
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  55.4
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  N-acetyl-2'-methyl-L-phenylalanine methyl ester 在 盐酸 作用下， 反应 6.0h， 以79%的产率得到2-methyl-L-phenylalanine hydrochloride
  参考文献：
  名称：

  Enantioselective Synthesis of a Phenylalanine Library Containing Alkyl Groups on the Aromatic Moiety: Confirmation of Stereostructure by X-Ray Analysis

  摘要：

  通过不对称氢化乙酰氨基丙烯酸酯衍生物，立体选择性地合成了六种含有2′-甲基-、2′,6′-二甲基-、2′-乙基-6′-甲基-、2′-异丙基-6′-甲基-、2′,4′,6′-三甲基-和3′,5′-二甲基-L-苯丙氨酸的苯丙氨酸类似物。酶解和X射线分析证实了所获得的苯丙氨酸衍生物的L构型。

  DOI：

  10.1248/cpb.54.873
• 作为产物：
  描述：

  methyl N-acetamido-3-o-methylphenylacrylate 在 (R)-Me-BIPAM 、 [Rh(cod)2]PF6 、 氢气 作用下， 以 二氯甲烷 为溶剂， 25.0 ℃ 、600.01 kPa 条件下， 反应 20.0h， 生成 N-acetyl-2'-methyl-L-phenylalanine methyl ester
  参考文献：
  名称：

  手性双齿亚磷酰胺（Me-BIPAM）用于Rh催化α-脱氢氨基酯，酰胺和衣康酸二甲酯的不对称加氢

  摘要：

  证明了Me-BIPAM对α-脱氢氨基酯，酰胺和衣康酸二甲酯的对映选择性氢化的高性能。[Rh（Me-BIPAM）（二烯）] X（二烯= cod，nbd; X = BF 4，PF 6，SbF 6）得到的旋光性β-芳基α-氨基酯含量高达ee的99％，1-芳基乙基胺含量高达在0.3-0.8 MPa的二氢和0.1-1 mol％的催化剂载量下，达到97％ee，具有90％ee的2-乙酰氨基丁酸甲酯和具有97％ee的2-甲基琥珀酸二甲酯。

  DOI：

  10.1016/j.tetlet.2008.12.086

文献信息

• Chiral bisphosphine ligands based on quinoline oligoamide foldamers: application in asymmetric hydrogenation
  作者：Lu Zheng、Dan Zheng、Yanru Wang、Chengyuan Yu、Kun Zhang、Hua Jiang

  DOI：10.1039/c9ob01649j

  日期：——

  A series of chiral bisphosphine ligands were designed and synthesized based on single-handed quinoline oligoamide foldamers. The bisphosphine ligands can coordinate with Rh(cod)2BF4 in a 1 : 1 stoichiometry and the resulted chiral Rh(I) catalysts were applied in the asymmetric hydrogenation of α-dehydroamino acid esters, in which excellent conversions and promising levels of enantioselectivity were

  基于单手喹啉寡酰胺折叠剂设计和合成了一系列手性双膦配体。双膦配体可以以1：1的化学计量比与Rh（cod）2 BF 4配位，并将所得的手性Rh（I）催化剂用于α-脱氢氨基酸酯的不对称加氢中，其中出色的转化率和对映选择性水平很有希望实现了。
• A chiral bidentate phosphoramidite (Me-BIPAM) for Rh-catalyzed asymmetric hydrogenation of α-dehydroamino esters, enamides, and dimethyl itaconate
  作者：Kazunori Kurihara、Yasunori Yamamoto、Norio Miyaura

  DOI：10.1016/j.tetlet.2008.12.086

  日期：2009.7

  High performance of Me-BIPAM for enantioselective hydrogenation of α-dehydroamino esters, enamides, and dimethyl itaconate was demonstrated. [Rh(Me-BIPAM)(diene)]X (diene = cod, nbd; X = BF4, PF6, SbF6) gave optically active β-aryl α-amino esters up to 99% ee, 1-arylethylamines up to 97% ee, methyl 2-acetylaminobutanoate with 90% ee, and dimethyl 2-methylsuccinate with 97% ee under 0.3−0.8 MPa dihydrogen

  证明了Me-BIPAM对α-脱氢氨基酯，酰胺和衣康酸二甲酯的对映选择性氢化的高性能。[Rh（Me-BIPAM）（二烯）] X（二烯= cod，nbd; X = BF 4，PF 6，SbF 6）得到的旋光性β-芳基α-氨基酯含量高达ee的99％，1-芳基乙基胺含量高达在0.3-0.8 MPa的二氢和0.1-1 mol％的催化剂载量下，达到97％ee，具有90％ee的2-乙酰氨基丁酸甲酯和具有97％ee的2-甲基琥珀酸二甲酯。
• Synthesis of Diastereomeric 1,4-Diphosphine Ligands Bearing Imidazolidin-2-one Backbone and Their Application in Rh(I)-Catalyzed Asymmetric Hydrogenation of Functionalized Olefins
  作者：Yong?Jian Zhang、Kee?Yong Kim、Jung?Hwan Park、Choong?Eui Song、Kyungae Lee、Myoung?Soo Lah、Sang-gi Lee

  DOI：10.1002/adsc.200404286

  日期：2005.3

  The diastereomeric 1,4-diphosphine ligands, (S,S,S,S)-1a, (R,S,S,R)-1b and (R,S,S,S)-1c, with the imidazolidin-2-one backbone were synthesized, and utilized for an investigation of the effects of backbone chirality on the enantioselectivity in the Rh(I)-catalyzed hydrogenation of various functionalized olefinic substrates. It was found that the catalytic efficiencies are largely dependent on the configurations

  非对映体1,4-二膦配体（S，S，S，S）-1a，（R，S，S，R）-1b和（R，S，S，S）-1c，含咪唑啉二-2合成一个骨架，并将其用于研究骨架手性对Rh（I）催化的各种官能化烯烃底物加氢中对映选择性的影响。已经发现，催化效率在很大程度上取决于α-碳到膦的构型。因此，伪c ^ 2 -symmetrical二膦，（- [R ，小号，小号，小号） - 1C，表明在基片，特别是在甲基α-的氢化的广谱的氢化优异的对映选择性（93.0-98.6％EES）（ñ -乙酰胺基）-β-芳基丙烯酸酯（95.3–97.0％ee）。但是，通过C 2对称的（R，S，S，R）-1b获得的对映选择性很大程度上取决于底物（19.8–97.3％ee）。配位体的铑配合物1a中具有（小号，小号，S，S）-构型显示了所有被检测底物的最低催化效率（0-84.8％ee）。
• Supramolecular chiral phosphorous ligands based on a [2]pseudorotaxane complex for asymmetric hydrogenation
  作者：Yong Li、Yu Feng、Yan-Mei He、Fei Chen、Jie Pan、Qing-Hua Fan

  DOI：10.1016/j.tetlet.2008.03.039

  日期：2008.4

  A new type of supramolecular chiral phosphorus-based ligands was prepared from easily available monodentate ligands through complexation between dibenzylammonium salt and dibenzo[24]crown-8 macrocycle. Rhodium complexes with these supramolecular ligands were prepared, and the supramolecular bidentate ligand-containing catalyst has demonstrated better catalytic activity for all substrates, and higher

  一种新型的超分子手性磷基配体是通过二苄基铵盐与二苯并[24] crown-8大环之间的络合，由易于获得的单齿配体制备的。制备了具有这些超分子配体的铑配合物，含α-超分子双齿配体的催化剂对所有底物均表现出更好的催化活性，除了邻位取代的底物比在α不对称氢化中从母体单齿配体获得的底物更高的对映选择性-脱氢氨基酸酯。
• Dendritic MonoPhos: synthesis and application in Rh-catalyzed asymmetric hydrogenation
  作者：Wei-Jun Tang、Yi-Yong Huang、Yan-Mei He、Qing-Hua Fan

  DOI：10.1016/j.tetasy.2006.01.013

  日期：2006.2

  A new class of dendritic monodentate phosphoramidite ligands were synthesized through substitution of the dimethylamino moiety in MonoPhos by the Frechet-type dendritic wedge and applied in the asymmetric hydrogenation of alpha-dehydroamino acid esters and dimethyl itaconate. High enantioselectivities (up to 97.9% ee) and catalytic activities (up to 4850 h(-1) TOF) were achieved, which are better or comparable to those obtained from MonoPhos. The third generation dendrimer catalyst gave the slightly lower catalytic activity relative to the lower generation ones. The steric shielding by the dendrimer could stabilize the rhodium complex against decomposition caused by hydrolysis in a protic solvent. The inactive catalysts (RhL3 and RhL4) were activated by addition of a free metal precursor Rh(COD)(2)BF4, and showed high enantioselectivities and catalytic activities. (c) 2006 Elsevier Ltd. All rights reserved.

表征谱图