syn-1,1-dimethylethyl 3-((benzylamino)methyl)-3-hydroxybutanoate

• 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: syn-1,1-dimethylethyl 3-((benzylamino)methyl)-3-hydroxybutanoate
• 英文别名: tert-butyl (2R,3R)-2-[(benzylamino)methyl]-3-hydroxybutanoate
• 化学式: C₁₆H₂₅NO₃
• 分子量: 279.379
• InChiKey: ARUMWTGKVDOLLZ-TZMCWYRMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  20
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  58.6
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  对硝基苯甲醛 、 syn-1,1-dimethylethyl 3-((benzylamino)methyl)-3-hydroxybutanoate 以 苯 为溶剂， 以63%的产率得到5,6-cis-5-((1,1-dimethylethoxy)carbonyl)-6-methyl-2-(4-nitrophenyl)-3-benzyltetrahydro-1,3-oxazine
  参考文献：
  名称：

  A Simple Route to .alpha.-Substituted-.beta.-Amino Ester Precursors of Carbapenem Antibiotics

  摘要：

  A three-step process is presented for the preparation of alpha-substituted-beta-amino esters which can serve as precursors to a key intermediate in carbapenem synthesis. The pivotal reaction in this sequence involves a highly diastereoselective conjugate addition reaction. Two series of alkenoates bearing a stereogenic substituent attached to C2 were prepared and their conjugate addition reactions with benzylamine studied under several different sets of conditions. Conjugate addition of benzylamine to alkenoates 7a and 7d, in methanol at room temperature, gave adducts 8a and Sd with virtually complete anti-diastereoselectivity. These two beta-amino esters bear the correct relative stereochemistry and side chain to serve as precursors for carbapenem antibiotic synthetic intermediates. The role of the allylic substituents of the alkenoates 7a-e in determining the stereochemical outcome of these additions is discussed. These conjugate additions were explored further by the preparation and conjugate addition reactions of the alpha,beta-disubstituted alkenoates 15a and 15b. It was found that the presence of a beta-substituent led to a dramatic reduction in yield although the same anti-diastereoselectivity was maintained. The relative stereochemistry of the adducts was established by examination of the relevant coupling constants in the H-1 NMR spectra of their tetrahydro-1,3-oxazine derivatives.

  DOI：

  10.1021/jo00125a043
• 作为产物：
  描述：

  tert-butyl 3-hydroxy-2-methylenebutanoate 、 苄胺 以 四氢呋喃 为溶剂， 反应 28.0h， 生成 anti-1,1-dimethylethyl 3-((benzylamino)methyl)-3-hydroxybutanoate 、 syn-1,1-dimethylethyl 3-((benzylamino)methyl)-3-hydroxybutanoate
  参考文献：
  名称：

  A Simple Route to .alpha.-Substituted-.beta.-Amino Ester Precursors of Carbapenem Antibiotics

  摘要：

  A three-step process is presented for the preparation of alpha-substituted-beta-amino esters which can serve as precursors to a key intermediate in carbapenem synthesis. The pivotal reaction in this sequence involves a highly diastereoselective conjugate addition reaction. Two series of alkenoates bearing a stereogenic substituent attached to C2 were prepared and their conjugate addition reactions with benzylamine studied under several different sets of conditions. Conjugate addition of benzylamine to alkenoates 7a and 7d, in methanol at room temperature, gave adducts 8a and Sd with virtually complete anti-diastereoselectivity. These two beta-amino esters bear the correct relative stereochemistry and side chain to serve as precursors for carbapenem antibiotic synthetic intermediates. The role of the allylic substituents of the alkenoates 7a-e in determining the stereochemical outcome of these additions is discussed. These conjugate additions were explored further by the preparation and conjugate addition reactions of the alpha,beta-disubstituted alkenoates 15a and 15b. It was found that the presence of a beta-substituent led to a dramatic reduction in yield although the same anti-diastereoselectivity was maintained. The relative stereochemistry of the adducts was established by examination of the relevant coupling constants in the H-1 NMR spectra of their tetrahydro-1,3-oxazine derivatives.

  DOI：

  10.1021/jo00125a043

文献信息

• A Simple Route to .alpha.-Substituted-.beta.-Amino Ester Precursors of Carbapenem Antibiotics
  作者：Patrick Perlmutter、Mark Tabone

  DOI：10.1021/jo00125a043

  日期：1995.10

  A three-step process is presented for the preparation of alpha-substituted-beta-amino esters which can serve as precursors to a key intermediate in carbapenem synthesis. The pivotal reaction in this sequence involves a highly diastereoselective conjugate addition reaction. Two series of alkenoates bearing a stereogenic substituent attached to C2 were prepared and their conjugate addition reactions with benzylamine studied under several different sets of conditions. Conjugate addition of benzylamine to alkenoates 7a and 7d, in methanol at room temperature, gave adducts 8a and Sd with virtually complete anti-diastereoselectivity. These two beta-amino esters bear the correct relative stereochemistry and side chain to serve as precursors for carbapenem antibiotic synthetic intermediates. The role of the allylic substituents of the alkenoates 7a-e in determining the stereochemical outcome of these additions is discussed. These conjugate additions were explored further by the preparation and conjugate addition reactions of the alpha,beta-disubstituted alkenoates 15a and 15b. It was found that the presence of a beta-substituent led to a dramatic reduction in yield although the same anti-diastereoselectivity was maintained. The relative stereochemistry of the adducts was established by examination of the relevant coupling constants in the H-1 NMR spectra of their tetrahydro-1,3-oxazine derivatives.