(Z)-2-acetylamino-4-methyl-pent-2-enoic acid methyl ester | 66299-28-3

• 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: (Z)-2-acetylamino-4-methyl-pent-2-enoic acid methyl ester
• 英文别名: (Z)-methyl 2-acetamido-4-methylpent-2-enoate；methyl 2-(acetylamino)-4-methylpent-2-enoate；(Z)-N-acetyl-dehydroleucine；Z-Methyl-α-acetylamino-β-isopropylacrylat；methyl (Z)-2-acetamido-4-methylpent-2-enoate
• CAS: 66299-28-3
• 化学式: C₉H₁₅NO₃
• 分子量: 185.223
• InChiKey: IZGZKVOFEFEJTR-YVMONPNESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  13
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.56
• 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：

  (Z)-2-acetylamino-4-methyl-pent-2-enoic acid methyl ester 在 1,2-bis[(2S,5S)-2,5-diethylphospholano]benzene(1,5-cyclooctadiene)rhodium(I) trifluoromethanesulfonate 、 氢气 作用下， 以 甲醇 为溶剂， 20.0~25.0 ℃ 、206.84 kPa 条件下， 以100%的产率得到N-乙酰-L-亮氨酸甲酯
  参考文献：
  名称：

  C2-symmetric bis(phospholanes) and their use in highly enantioselective hydrogenation reactions

  摘要：

  DOI：

  10.1021/ja00022a047
• 作为产物：
  描述：

  5-甲氧基-2-甲基-1,3-恶唑 在 盐酸 作用下， 以 二氯甲烷 、 苯 为溶剂， 反应 52.0h， 生成 (Z)-2-acetylamino-4-methyl-pent-2-enoic acid methyl ester
  参考文献：
  名称：

  Synthesis of erythro-α-Amino β-hydroxy Carboxylic Acid Esters by Diastereoselective Photocycloaddition of 5-Methoxyoxazoles with Aldehydes

  摘要：

  A new photoaldol route to alpha-amino-beta-hydroxy carboxylic acid esters is initiated by the photocycloaddition of aromatic or aliphatic aldehydes to 5-methoxyoxazoles. The 4-unsubstituted 5-methyloxazole 1 gave the cycloadducts 8a-f in high yields and excellent exo-diastereoselectivities. Hydrolysis of 8a-f gives the N-acetyl alpha-amino-beta-hydroxy esters 9a-f, which could be subsequently converted into the corresponding Z-didehydro alpha-amino acids 10a-f. Quartenary alpha-amino-beta-hydroxy esters 12, 14, 16, 18, and 20, which are stable against dehydration, were obtained from the 4-alkylated 5-methoxyoxazoles 2-6, in most cases highly erythro-selective due to the high degree of stereocontrol (exo) at the photocycloaddition (to give 11, 13, 15, 17, and 19) level. The relative configurations of the N-acetyl alpha-amino-beta-hydroxy esters were determined by NMR spectroscopy and comparison with chiral pool-derived compounds as well as by X-ray structure determination of the ester 23, formed by hydrolysis of the cycloadduct 22, derived from photocycloaddition of propionaldehyde to the isoleucine-derived oxazole 21.

  DOI：

  10.1021/jo034830h

文献信息

• Asymmetric conjugate reductions with samarium diiodide: asymmetric synthesis of (2S,3R)- and (2S,3S)-[2-²H,3-²H]-leucine-(S)-phenylalanine dipeptides and (2S,3R)-[2-²H,3-²H]-phenylalanine methyl ester
  作者：Stephen G. Davies、Humberto Rodríguez-Solla、Juan A. Tamayo、Andrew R. Cowley、Carmen Concellón、A. Christopher Garner、Alastair L. Parkes、Andrew D. Smith

  DOI：10.1039/b500566c

  日期：——

  diastereoselective samarium diiodide and D(2)O-promoted conjugate reduction of homochiral (E)- and (Z)-benzylidene and isobutylidene diketopiperazines (E)-5,7 and (Z)-6,8 has been demonstrated. This methodology allows the asymmetric synthesis of methyl (2S,3R)-dideuteriophenylalanine 27 in > or = 95% de and >98% ee, and (2S,3R)- or (2S,3S)-dideuterioleucine-(S)-phenylalanine dipeptides 37 and 38 in moderate de,

  已经证明了高度非对映选择性的二碘化and和D（2）O促进的同手性（E）-和（Z）-亚苄基和异丁烯二酮哌嗪（E）-5,7和（Z）-6,8的共轭还原。这种方法学允许不对称合成95％de和98％ee或以下的（2S，3R）-或（2S，3S）-二氘代亮氨酸-（S）-苯丙氨酸的甲基（2S，3R）-二氘代苯丙氨酸二肽37和38分别处于中等水平，分别为66％和74％。提出了一种机制来说明此过程。
• Catalytic Asymmetric Hydrogenation of<b><i>α</i></b>-(Acetamido)acrylates Using TRAP Trans-Chelating Chiral Bisphosphine Ligands: Remarkable Effects of Ligand<b><i>P</i></b>-Substituent and Hydrogen Pressure on Enantioselectivity
  作者：Ryoichi Kuwano、Masaya Sawamura、Yoshihiko Ito

  DOI：10.1246/bcsj.73.2571

  日期：2000.11

  β-substituent and the ligand P-substituent as well as decreasing hydrogen pressure. The selectivity for the (R)-product in the reaction with EtTRAP-rhodium catalyst at 60 °C and 0.5 kg cm-2 of hydrogen pressure was as follows: R = H, 96% ee; R = Me, 92% ee; R = Ph, 77% ee; R = i-Pr, 57% ee. The remarkable steric and pressure effects caused a dramatic reversal of enantioselectivity in the reaction of methyl

  用 [Rh(cod)2]BF4 和反式螯合手性双膦配体 (S,S)-2,2'-双 [( R)-1-(二烷基膦基)乙基]-1,1'-二茂铁[(R,R)-(S,S)-TRAPs]。在β-未取代或β-单取代的α-(乙酰氨基)丙烯酸酯[(E)-RCH=C(NHAc)CO2Me]的反应中，(R)-氢化产物的选择性随着底物β-空间需求的降低而增加取代基和配体 P 取代基以及降低氢压。在 60 °C 和 0.5 kg cm-2 氢气压力下与 EtTRAP-铑催化剂反应的 (R)-产物的选择性如下：R = H，96% ee；R = Me，92% ee；R = Ph，77% ee；R = i-Pr，57% ee。显着的空间和压力效应导致 2-(N-乙酰氨基) 肉桂酸甲酯 (R = Ph) 反应中对映选择性的显着逆转。例如，在 60 °C 和 0.1 kg cm-2 氢气压力下使用 EtTRAP 的选择性为 87%
• Application of Chiral Mixed Phosphorus/Sulfur Ligands to Enantioselective Rhodium-Catalyzed Dehydroamino Acid Hydrogenation and Ketone Hydrosilylation Processes
  作者：David A. Evans、Forrest E. Michael、Jason S. Tedrow、Kevin R. Campos

  DOI：10.1021/ja012639o

  日期：2003.3.1

  Rh-catalyzed dehydroamino acid hydrogenation and ketone hydrosilylation reactions (eqs 1, 2). After assaying the influence of the substituents at sulfur, the substituents on the ligand backbone, the relative stereochemistry within the ligand backbone, and the substituents at phosphorus, ligands 2c (R = 3,5-dimethylphenyl) and 3 were found to be optimal in the Rh-catalyzed hydrogenation of a variety of alpha-acylaminoacrylates

  手性混合磷/硫配体 1-3 已被证明在对映选择性 Rh 催化的脱氢氨基酸氢化和酮氢化硅烷化反应中有效（方程式 1、2）。在测定硫上的取代基、配体骨架上的取代基、配体骨架内的相对立体化学以及磷上的取代基的影响后，发现配体 2c (R = 3,5-二甲基苯基) 和 3 在以高对映选择性 (89-97% ee) 对各种 α-酰基氨基丙烯酸酯进行 Rh 催化氢化。对用于 Rh 催化的酮氢化硅烷化的催化剂进行类似的优化表明，配体 3 为各种芳烷基和二烷基酮提供了最高的对映选择性（高达 99% ee）。
• Highly enantioselective synthesis of non-natural aliphatic α-amino acids via asymmetric hydrogenation
  作者：Jianjian Ji、Caiyou Chen、Jiayu Cai、Xinrui Wang、Kai Zhang、Liyang Shi、Hui Lv、Xumu Zhang

  DOI：10.1039/c5ob01111f

  日期：——

  hydrogenated in a highly efficient and enantioselective way. Excellent enantioselectivities together with excellent yields were achieved for a series of substrates. An efficient approach for the synthesis of the intermediate of the orally administered anti-diabetic drugs Alogliptin and Linagliptin in the DPP-4 inhibitor class was also developed.

  通过使用铑-双膦配合物作为催化剂，β-烷基（Z）-N-乙酰基脱氢氨基酯以高效和对映选择性的方式平稳氢化。对于一系列底物，获得了优异的对映选择性和优异的产率。还开发了一种合成口服DPP-4抑制剂类抗糖尿病药物阿格列汀和利格列汀的中间体的有效方法。
• Synthesis and Synthetic Applications of α,β-Dideuterio-α-amino Esters Promoted by Samarium Diiodide
  作者：José Concellón、Humberto Rodríguez-Solla、Carmen Concellón、Paula Tuya

  DOI：10.1055/s-2008-1032063

  日期：2008.2

  A new, easy, and high-yielded route to isotopically labeled amino acid derivatives is reported. This process takes place through a SmI2-promoted 1,4-reduction of a variety of dehydro­amino esters in the presence of D2O. The dideuterio amino esters were transformed into other dideuterated compounds such as a-amino acids and 1,2-amino alcohols. A mechanism to explain the 1,4-reduction process is also proposed.

  报道了一种新的、简单的、高产率的同位素标记氨基酸衍生物合成路线。该过程通过SmI2催化的以D2O为反应介质的1,4还原反应，对多种去氢氨基酯进行处理。双氘氨基酯被转化为其他双氘化合物，如α-氨基酸和1,2-氨基醇。还提出了一种机制来解释该1,4还原过程。