(R)-methyl 2-acetylamino-3-(2-thienyl)propanoate | 83396-81-0

• 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: (R)-methyl 2-acetylamino-3-(2-thienyl)propanoate
• 英文别名: methyl (2R)-2-acetamido-3-thiophen-2-ylpropanoate
• CAS: 83396-81-0
• 化学式: C₁₀H₁₃NO₃S
• 分子量: 227.284
• InChiKey: LHZZRXKRWQSIAY-SECBINFHSA-N

物化性质

• 沸点：
  397.8±32.0 °C(Predicted)
• 密度：
  1.211±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  15
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  83.6
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (R)-methyl 2-acetylamino-3-(2-thienyl)propanoate 在 盐酸 作用下， 反应 6.0h， 生成 3-(2-噻吩基)-D-丙氨酸
  参考文献：
  名称：

  Unusual amino acids IV. Asymmetric synthesis of thienylalanines

  摘要：

  (Z)-2-N-Acylamino-3-thienyl-acrylic acids and their esters were prepared by known procedures and hydrogenated to the corresponding optically active 2-N-acetyl(or benzoyl)-3-(2- or 3-thienyl)-alanines with optical yields up to 90 % using the rhodium complexes of ''PROPRAPHOS'' 6a,b and O,N-bis(diphenylphosphino)-2-exo-hydroxy,3-endo-methylamino-norbornane 6c as chiral catalysts, Recrystallization and deacylation of the obtained amino acid derivatives yields the optically pure hydrochlorides of the thienylalanines and the free amino acids.

  DOI：

  10.1016/s0957-4166(00)80424-3
• 作为产物：
  描述：

  (Z)-2-Methyl-5-oxo-4-(2-thienylmethylene)-4,5-dihydro-1,3-oxazole 在 (+)-(S)-PROPRAPHOS rhodium 、 氢气 作用下， 以 甲醇 为溶剂， 25.0 ℃ 、101.33 kPa 条件下， 生成 (R)-methyl 2-acetylamino-3-(2-thienyl)propanoate
  参考文献：
  名称：

  Unusual amino acids IV. Asymmetric synthesis of thienylalanines

  摘要：

  (Z)-2-N-Acylamino-3-thienyl-acrylic acids and their esters were prepared by known procedures and hydrogenated to the corresponding optically active 2-N-acetyl(or benzoyl)-3-(2- or 3-thienyl)-alanines with optical yields up to 90 % using the rhodium complexes of ''PROPRAPHOS'' 6a,b and O,N-bis(diphenylphosphino)-2-exo-hydroxy,3-endo-methylamino-norbornane 6c as chiral catalysts, Recrystallization and deacylation of the obtained amino acid derivatives yields the optically pure hydrochlorides of the thienylalanines and the free amino acids.

  DOI：

  10.1016/s0957-4166(00)80424-3

文献信息

• Chiral bisphospholane ligands (Me-ketalphos): synthesis of their Rh(I) complexes and applications in asymmetric hydrogenation
  作者：Qian Dai、Chun-Jiang Wang、Xumu Zhang

  DOI：10.1016/j.tet.2005.10.047

  日期：2006.1

  Rhodium complexes of functionalized bisphospholane ligands (S,S,S,S-Me-ketalphos) 1 and (R,S,S,R-Me-ketalphos) 2 have been used as catalyst precursors for the asymmetric hydrogenation of several different types of functionalized olefins and have achieved high enantioselectivities.

  功能化双膦烷配体（S，S，S，S -Me-ketalphos）1和（R，S，S，R -Me-ketalphos）2的铑配合物已被用作催化剂前体，用于几种不同类型的不对称氢化官能化的烯烃，并实现了高对映选择性。
• Asymmetric Reduction of Aromatic α-Dehydroamino Acid Esters with Water as Hydrogen Source
  作者：Yuze Dai、Jingchao Chen、Zheting Wang、Ting Wang、Lin Wang、Yong Yang、Xingfang Qiao、Baomin Fan

  DOI：10.1021/acs.joc.1c00426

  日期：2021.5.21

  The asymmetric reduction of aromatic α-dehydroamino acid esters with water as the hydrogen source was developed by a Rh/Cu co-catalytic system. The reaction tolerates various functional groups, providing a valuable synthetic tool to access chiral α-amino acid esters readily. Moreover, the present methodology also was applied in the cost-effective and easy to handle preparation of chiral deuterated

  通过Rh / Cu共催化体系开发了以水为氢源的芳香族α-脱氢氨基酸酯的不对称还原反应。该反应可耐受各种官能团，从而提供了一种有价值的合成工具，可轻松获得手性α-氨基酸酯。此外，本方法学还用于通过使用D 2 O的经济高效且易于处理的手性氘代α-氨基酯的制备中。
• Novel phosphine-phosphite and phosphine-phosphinite ligands for highly enantioselective asymmetric hydrogenation
  作者：Yongjun Yan、Yongxiang Chi、Xumu Zhang

  DOI：10.1016/j.tetasy.2004.04.013

  日期：2004.7

  Two novel phosphine-phosphite (S,R)-o-BINAPHOS and phosphine-phosphinite (S)-o-BIPNITE ligands based on ortho phenyl substituted (S)-BINOL have been synthesized. Extremely high enantioselectivity (over 99% ee in most cases) has been achieved for the Rh-catalyzed asymmetric hydrogenation of α-dehydroamino acid derivatives.

  两种新型膦-亚磷酸酯（小号，- [R ）- ö -BINAPHOS和膦-次亚膦酸酯（小号） - ö -BIPNITE配体基于邻苯基取代的（小号）-BINOL已经合成。Rh催化α-脱氢氨基酸衍生物的不对称氢化反应，具有极高的对映选择性（大多数情况下，ee超过99％）。
• Novel, Tunable, and Efficient Chiral Bisdihydrobenzooxaphosphole Ligands for Asymmetric Hydrogenation
  作者：Wenjun Tang、Bo Qu、Andrew G. Capacci、Sonia Rodriguez、Xudong Wei、Nizar Haddad、Bikashandarkoil Narayanan、Shengli Ma、Nelu Grinberg、Nathan K. Yee、Dhileep Krishnamurthy、Chris H. Senanayake

  DOI：10.1021/ol9025815

  日期：2010.1.1

  A series of novel, efficient, air-stable, and tunable chiral bisdihydrobenzooxaphosphole ligands (BIBOPs) were developed for rhodium-catalyzed hydrogenations of various functionalized olefins such as alpha-arylenamides, alpha-(acylamino)acrylic acid derivatives, beta-(acylamino)acrylates, and dimethyl itaconate with excellent enantioselectivities (up to 99% ee) and reactivities (up to 2000 TON).
• Carbohydrate Phosphinites as Practical Ligands in Asymmetric Catalysis:  Electronic Effects and Dependence of Backbone Chirality in Rh-Catalyzed Asymmetric Hydrogenations. Synthesis of <i>R</i>- or <i>S</i>-Amino Acids Using Natural Sugars as Ligand Precursors
  作者：T. V. RajanBabu、Timothy A. Ayers、Gary A. Halliday、Kimberly K. You、Joseph C. Calabrese

  DOI：10.1021/jo970884d

  日期：1997.8.1

  Vicinal diarylphosphinites derived from carbohydrates are excellent ligands for the Rh(I)-catalyzed enantioselective asymmetric hydrogenation of dehydroamino acid derivatives, producing the highest enantioselectivity of any ligands directly prepared from natural products. The enantioselectivity can be enhanced by the appropriate choice of substituents on the aromatic rings of the phosphinites. For example, the use of phosphinites with electron-donating bis(3,5-dimethylphenyl) groups on phosphorus provides ee's up to 99% for a wide range of amino acids including some with easily removable N-protecting groups. Electron-withdrawing aryl substituents, on the other hand, decrease the enantioselectivity. Sense of chiral induction in the amino acid product depends on the relative juxtaposition of the vicinal diphosphinites on a given sugar backbone. When readily available D-glucopyranosides are used as the starting sugars, 2,3-phosphinites give the S-amino acids and 3,4-phosphinites give the R-amino acids. In the case of aromatic and heteroaromatic amino acids, enantioselectivities > 95% are consistently obtained. Practical considerations such as the ease of ligand synthesis, rates of reactions, catalyst turnover, and scope and limitations in terms of substrates are discussed. A possible explanation for the enhancement of enantioselectivity by electron-rich phosphinites is offered.