(-)-benzyl-3,4-bis[(3S)-3-[bis-(tert-butylcarbonyl)amino]-4-(tert-butoxy)-4-oxobutyl]-1H-pyrrole-2-carboxylate | 257883-69-5

• 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: (-)-benzyl-3,4-bis[(3S)-3-[bis-(tert-butylcarbonyl)amino]-4-(tert-butoxy)-4-oxobutyl]-1H-pyrrole-2-carboxylate
• 英文别名: benzyl 3,4-bis[(3S)-3-[bis[(2-methylpropan-2-yl)oxycarbonyl]amino]-4-[(2-methylpropan-2-yl)oxy]-4-oxobutyl]-1H-pyrrole-2-carboxylate
• CAS: 257883-69-5
• 化学式: C₄₈H₇₃N₃O₁₄
• 分子量: 916.119
• InChiKey: JSWVEACJJGXTKZ-HEVIKAOCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.6
• 重原子数：
  65
• 可旋转键数：
  26
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.65
• 拓扑面积：
  206
• 氢给体数：
  1
• 氢受体数：
  14

反应信息

• 作为反应物：
  描述：

  (S)-(-)-tert-butyl-2-[bis-(tert-butylcarbonyl)amino]-6-iodohexanoate 、 (-)-benzyl-3,4-bis[(3S)-3-[bis-(tert-butylcarbonyl)amino]-4-(tert-butoxy)-4-oxobutyl]-1H-pyrrole-2-carboxylate 在 18-冠醚-6 、 potassium tert-butylate 作用下， 以 四氢呋喃 为溶剂， 反应 7.0h， 以42%的产率得到(-)-benzyl-3,4-bis[(3S)-3-[bis-(tert-butylcarbonyl)amino]-4-(tert-butoxy)-4-oxobutyl]-1-[(5S)-5-[bis(tert-butoxycarbonyl)amino]-6-(tert-butoxy)-6-oxohexyl]-1H-pyrrole-2-carboxylate
  参考文献：
  名称：

  Bone Collagen Cross-Links:  A Convergent Synthesis of (+)-Deoxypyrrololine

  摘要：

  A convergent total synthesis of (+)-deoxypyrrololine (Dpl, 4), a putative cross-link of bone collagen, is described starting from a commercially available L-glutamic acid derivative, (4S)-5-(tert-butoxy)47[(tert-butoxycarbonyl)amino]-5-oxopentanic acid (16). Condensation of aldehyde (S)-(-)-17 with nitro compound (S)-(-)-27, both of which were prepared from a common precursor (S)-16, gave the alpha -hydroxynitro compound 28, which upon; acetylation afforded alpha -acetoxynitro compound,14 in good yield. Subsequent condensation and cyclization of a-acetoxynitro compound 14 with benzyl isocyanoacetate (15) in the presence of DBU in THF gave the key pyrrole intermediate (S,S)-(-)-12 in 57% yield. N-Alkylation of pyrrole (S,S)-(-)-12 with iodide (S)-(-)-13 using t-BuOK in THF afforded the 2-benzyloxycarbonyl-1,3,4-substituted pyrrole derivative (-)-29 in 42% yield. Removal of the protective groups in (-)-29 followed by hydrogenolysis and decarboxylation afforded the cross-link (+)-Dpl (4) in good overall yield. The synthesis of an analogue (S)-(+)-24 ana formation of a novel tetrahydroindole derivative(-)-31 are also described.

  DOI：

  10.1021/jo0008901
• 作为产物：
  描述：

  氰基乙酸苄酯 、 1,10-di-tert-butyl-6-O-acetyl-2,9-bis[bis-(tert-butylcarbonyl)amino]-2,3,4,5,7,9-heptadeoxy-5-nitro-D-threo-decarate 在 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 四氢呋喃 为溶剂， 以57%的产率得到(-)-benzyl-3,4-bis[(3S)-3-[bis-(tert-butylcarbonyl)amino]-4-(tert-butoxy)-4-oxobutyl]-1H-pyrrole-2-carboxylate
  参考文献：
  名称：

  Bone Collagen Cross-Links:  A Convergent Synthesis of (+)-Deoxypyrrololine

  摘要：

  A convergent total synthesis of (+)-deoxypyrrololine (Dpl, 4), a putative cross-link of bone collagen, is described starting from a commercially available L-glutamic acid derivative, (4S)-5-(tert-butoxy)47[(tert-butoxycarbonyl)amino]-5-oxopentanic acid (16). Condensation of aldehyde (S)-(-)-17 with nitro compound (S)-(-)-27, both of which were prepared from a common precursor (S)-16, gave the alpha -hydroxynitro compound 28, which upon; acetylation afforded alpha -acetoxynitro compound,14 in good yield. Subsequent condensation and cyclization of a-acetoxynitro compound 14 with benzyl isocyanoacetate (15) in the presence of DBU in THF gave the key pyrrole intermediate (S,S)-(-)-12 in 57% yield. N-Alkylation of pyrrole (S,S)-(-)-12 with iodide (S)-(-)-13 using t-BuOK in THF afforded the 2-benzyloxycarbonyl-1,3,4-substituted pyrrole derivative (-)-29 in 42% yield. Removal of the protective groups in (-)-29 followed by hydrogenolysis and decarboxylation afforded the cross-link (+)-Dpl (4) in good overall yield. The synthesis of an analogue (S)-(+)-24 ana formation of a novel tetrahydroindole derivative(-)-31 are also described.

  DOI：

  10.1021/jo0008901

文献信息

• Total Synthesis of (+)-Deoxypyrrololine: A Potential Biochemical Marker for Diagnosis of Osteoporosis
  作者：Maciej Adamczyk、Donald D. Johnson、Rajarathnam E. Reddy

  DOI：10.1002/(sici)1521-3773(19991203)38:23<3537::aid-anie3537>3.0.co;2-r

  日期：——
• Bone Collagen Cross-Links:  A Convergent Synthesis of (+)-Deoxypyrrololine
  作者：Maciej Adamczyk、Donald D. Johnson、Rajarathnam E. Reddy

  DOI：10.1021/jo0008901

  日期：2001.1.1

  A convergent total synthesis of (+)-deoxypyrrololine (Dpl, 4), a putative cross-link of bone collagen, is described starting from a commercially available L-glutamic acid derivative, (4S)-5-(tert-butoxy)47[(tert-butoxycarbonyl)amino]-5-oxopentanic acid (16). Condensation of aldehyde (S)-(-)-17 with nitro compound (S)-(-)-27, both of which were prepared from a common precursor (S)-16, gave the alpha -hydroxynitro compound 28, which upon; acetylation afforded alpha -acetoxynitro compound,14 in good yield. Subsequent condensation and cyclization of a-acetoxynitro compound 14 with benzyl isocyanoacetate (15) in the presence of DBU in THF gave the key pyrrole intermediate (S,S)-(-)-12 in 57% yield. N-Alkylation of pyrrole (S,S)-(-)-12 with iodide (S)-(-)-13 using t-BuOK in THF afforded the 2-benzyloxycarbonyl-1,3,4-substituted pyrrole derivative (-)-29 in 42% yield. Removal of the protective groups in (-)-29 followed by hydrogenolysis and decarboxylation afforded the cross-link (+)-Dpl (4) in good overall yield. The synthesis of an analogue (S)-(+)-24 ana formation of a novel tetrahydroindole derivative(-)-31 are also described.