tert-butyl (3R,4S)-3-[(1S)-2-methyl-1-(phenylmethoxycarbonylamino)propyl]-2-oxo-4-phenylazetidine-1-carboxylate | 193148-98-0

• 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: tert-butyl (3R,4S)-3-[(1S)-2-methyl-1-(phenylmethoxycarbonylamino)propyl]-2-oxo-4-phenylazetidine-1-carboxylate
• CAS: 193148-98-0
• 化学式: C₂₆H₃₂N₂O₅
• 分子量: 452.55
• InChiKey: RXRROJCWSQGNNE-BHIFYINESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.3
• 重原子数：
  33
• 可旋转键数：
  9
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  84.9
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  吗啉 、 tert-butyl (3R,4S)-3-[(1S)-2-methyl-1-(phenylmethoxycarbonylamino)propyl]-2-oxo-4-phenylazetidine-1-carboxylate 反应 1.5h， 以72%的产率得到(2R,3S,1'S)-3-benzyloxycarbonylamino-2-((tert-butyloxycarbonylamino)(phenyl)methyl)-4-methyl-1-(morpholin-4-yl)pentan-1-one
  参考文献：
  名称：

  通过亲核试剂的开环从α-氨基酸衍生的β-内酰胺合成β，β'-二氨基酸。在拟肽合成中的应用

  摘要：

  受保护的3-氨基烷基取代的氮杂环丁烷-2-酮与O-，N-或S-亲核试剂的开环分别导致β，β'-二氨基羧酸酯，酰胺和硫代酯。通过加入催化量的叠氮化钠可改善反应结果。可以使用具有未保护的氨基官能团的亲核试剂的甘氨酸衍生物。当使用体积较大的氨基酸酯时，中间体叠氮化物发生Curtius重排。形成的异辛酸酯被捕获为相应的脲衍生物。β-内酰胺酰胺部分的还原产生二氨基醇。

  DOI：

  10.1016/j.tet.2008.07.006
• 作为产物：
  描述：

  benzyl (S)-(1-diazo-4-methyl-2-oxopentan-3-yl)carbamate 在 4-二甲氨基吡啶 、 dipotassium hydrogenphosphate 、 dipotassium peroxodisulfate 、 三乙胺 作用下， 以 乙醚 、 二氯甲烷 、 水 、 乙腈 为溶剂， 反应 9.17h， 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

文献信息

• Synthesis of β,β′-Diamino Acids from α-Amino Acid Derived β-Lactams
  作者：Joachim Podlech、Alexander Taubinger、Dieter Fenske

  DOI：10.1055/s-2008-1032079

  日期：——

  Ring opening of protected 3-aminoalkyl-substituted azetidin-2-ones with 0-, N-, or S-nucleophiles led to β,β'-diaminocarboxylic esters, amides, and thioesters, respectively. The reaction outcome is improved by addition of catalytic amounts of sodium azide. Reduction of the β-lactam amide moiety led to diamino alcohols.

  受保护的 3-氨基烷基取代的氮杂环丁烷-2-酮与 0-、N-或 S-亲核试剂的开环分别产生 β,β'-二氨基羧酸酯、酰胺和硫酯。通过加入催化量的叠氮化钠改善反应结果。β-内酰胺酰胺部分的还原导致二氨基醇。
• 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.
• Synthesis of β,β′-diamino acids from α-amino acid-derived β-lactams by ring opening with nucleophiles. Utilization in the synthesis of peptidomimetics
  作者：Alexander A. Taubinger、Dieter Fenske、Joachim Podlech

  DOI：10.1016/j.tet.2008.07.006

  日期：2008.9

  d azetidin-2-ones with O-, N- or S-nucleophiles led to β,β′-diaminocarboxylic esters, amides and thioesters, respectively. The reaction outcome is improved by the addition of catalytic amounts of sodium azide. Utilization of a glycine derivative with unprotected amino function as nucleophile was possible. When bulkier amino acid esters were used, the intermediate acid azide underwent a Curtius rearrangement

  受保护的3-氨基烷基取代的氮杂环丁烷-2-酮与O-，N-或S-亲核试剂的开环分别导致β，β'-二氨基羧酸酯，酰胺和硫代酯。通过加入催化量的叠氮化钠可改善反应结果。可以使用具有未保护的氨基官能团的亲核试剂的甘氨酸衍生物。当使用体积较大的氨基酸酯时，中间体叠氮化物发生Curtius重排。形成的异辛酸酯被捕获为相应的脲衍生物。β-内酰胺酰胺部分的还原产生二氨基醇。