benzyl N-[(1S)-1-[(3R,4S)-1-[(4-methoxyphenyl)methyl]-2-oxo-4-phenylazetidin-3-yl]-2-methylpropyl]carbamate | 193148-89-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酰胺类
• 英文名称: benzyl N-[(1S)-1-[(3R,4S)-1-[(4-methoxyphenyl)methyl]-2-oxo-4-phenylazetidin-3-yl]-2-methylpropyl]carbamate
• CAS: 193148-89-9
• 化学式: C₂₉H₃₂N₂O₄
• 分子量: 472.584
• InChiKey: FVQIHBLFJRUYOI-KWXIBIRDSA-N

物化性质

• 沸点：
  672.9±55.0 °C(Predicted)
• 密度：
  1.181±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.6
• 重原子数：
  35
• 可旋转键数：
  10
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  67.9
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  benzyl N-[(1S)-1-[(3R,4S)-1-[(4-methoxyphenyl)methyl]-2-oxo-4-phenylazetidin-3-yl]-2-methylpropyl]carbamate 在 4-二甲氨基吡啶 、 dipotassium hydrogenphosphate 、 dipotassium peroxodisulfate 、 三乙胺 作用下， 以 二氯甲烷 、 水 、 乙腈 为溶剂， 反应 7.17h， 生成 tert-butyl (3R,4S)-3-[(1S)-2-methyl-1-(phenylmethoxycarbonylamino)propyl]-2-oxo-4-phenylazetidine-1-carboxylate
  参考文献：
  名称：

  Cycloadditions of Ketenes Generated in the Wolff Rearrangement. Stereoselective Synthesis of Aminoalkyl-Substituted β-Lactams from α-Amino Acids

  摘要：

  Diazo ketones 1-16, derived from suitable protected amino acids (Ala, Leu, Val, Ile, Tie, Phe, Pro, Orn, Lys, Ser, and Thr), have been photochemically rearranged, leading to the corresponding ketene intermediates. They were trapped with N-benzylbenzaldimine 17 to give beta-lactams S-SS in up to 90% yield. In these cycloadditions, two of the four possible diastereoisomers were formed exclusively. The selectivity ranged from 60:40 to 93:7 and the bulkiness of the parent amino acid side chain is the governing factor. The relative configuration was-proved by three X-ray crystal structures. The diastereoselectivity in these reactions is also influenced by the use of chiral N-phenethylbenzaldimines 34 and 35. With regard to a projected deprotection of the lactam-nitrogen, N-allyl- (49) and N-(p-methoxybenzyl)benzaldimine (44) were used in this reaction. This led to the N-allyl beta-lactams 50 and 51 in 62 and 56% yield, respectively, and to the p-methoxybenzyl-substituted beta-lactams 45 and 46 (50 and 72% yield). The p-methoxybenzyl, group on the valine-derived beta-lactam 45a can be cleaved with potassium peroxodisulfate in 63% yield.

  DOI：

  10.1021/jo9705069
• 作为产物：
  描述：

  benzyl (S)-(1-diazo-4-methyl-2-oxopentan-3-yl)carbamate 、 (E)-N-benzylidene-1-(4-methoxyphenyl)methanamine 以 乙醚 为溶剂， 反应 1.5h， 生成 benzyl N-[(1S)-1-[(3S,4R)-1-[(4-methoxyphenyl)methyl]-2-oxo-4-phenylazetidin-3-yl]-2-methylpropyl]carbamate 、 benzyl N-[(1S)-1-[(3R,4S)-1-[(4-methoxyphenyl)methyl]-2-oxo-4-phenylazetidin-3-yl]-2-methylpropyl]carbamate
  参考文献：
  名称：

  A Chiral, Oxidatively Cleavable Auxiliary in β-Lactam Synthesis - Double Diastereocontrol with p-Methoxyphenethyl-Substituted Imines

  摘要：

  本文介绍了一种用于斯陶丁格反应的新型手性、可氧化去除的助剂。当由适当保护的氨基酸制备的重氮酮 1-3 与对甲氧基苯乙基（PMPE）取代的亚胺反应时，生成了相应的反式取代的δ-内酰胺 7 和 8a-h。与非手性对甲氧基苄基（PMB）取代的亚胺相比，(S)-亚胺 5 通过双立体选择提高了选择性；因此，(R)-亚胺 4 的异构体比例降低。硝酸铈铵 (CAN) 可以去除辅助剂。

  DOI：

  10.1055/s-1999-3440

文献信息

• Cycloadditions of Ketenes Generated in the Wolff Rearrangement. Stereoselective Synthesis of Aminoalkyl-Substituted β-Lactams from α-Amino Acids
  作者：Joachim Podlech、Michael R. Linder

  DOI：10.1021/jo9705069

  日期：1997.8.1

  Diazo ketones 1-16, derived from suitable protected amino acids (Ala, Leu, Val, Ile, Tie, Phe, Pro, Orn, Lys, Ser, and Thr), have been photochemically rearranged, leading to the corresponding ketene intermediates. They were trapped with N-benzylbenzaldimine 17 to give beta-lactams S-SS in up to 90% yield. In these cycloadditions, two of the four possible diastereoisomers were formed exclusively. The selectivity ranged from 60:40 to 93:7 and the bulkiness of the parent amino acid side chain is the governing factor. The relative configuration was-proved by three X-ray crystal structures. The diastereoselectivity in these reactions is also influenced by the use of chiral N-phenethylbenzaldimines 34 and 35. With regard to a projected deprotection of the lactam-nitrogen, N-allyl- (49) and N-(p-methoxybenzyl)benzaldimine (44) were used in this reaction. This led to the N-allyl beta-lactams 50 and 51 in 62 and 56% yield, respectively, and to the p-methoxybenzyl-substituted beta-lactams 45 and 46 (50 and 72% yield). The p-methoxybenzyl, group on the valine-derived beta-lactam 45a can be cleaved with potassium peroxodisulfate in 63% yield.
• A Chiral, Oxidatively Cleavable Auxiliary in β-Lactam Synthesis - Double Diastereocontrol with p-Methoxyphenethyl-Substituted Imines
  作者：Joachim Podlech、Steffen Steurer

  DOI：10.1055/s-1999-3440

  日期：1999.4

  A new chiral, oxidatively removable auxiliary for the Staudinger reaction is presented. When diazo ketones 1-3 prepared from suitably protected amino acids reacted with p-methoxyphenethyl (PMPE)-substituted imines, the corresponding trans-substituted β-lactams 7 and 8a-h were formed. With the (S)-configured imine 5, an improvement of the selectivities is observed in comparison with achiral p-methoxybenzyl (PMB)-substituted imines by double stereoselection; consequently, the ratio of isomers decreased with the (R)-imine 4. The auxiliary could be removed with cerium ammonium nitrate (CAN).

  本文介绍了一种用于斯陶丁格反应的新型手性、可氧化去除的助剂。当由适当保护的氨基酸制备的重氮酮 1-3 与对甲氧基苯乙基（PMPE）取代的亚胺反应时，生成了相应的反式取代的δ-内酰胺 7 和 8a-h。与非手性对甲氧基苄基（PMB）取代的亚胺相比，(S)-亚胺 5 通过双立体选择提高了选择性；因此，(R)-亚胺 4 的异构体比例降低。硝酸铈铵 (CAN) 可以去除辅助剂。