Boc-β^2,2-HAc³c-β^2,2-HAc³c-β^2,2,-HAc³c-β^2,2,-HAc³c-β^2,2-HAc³c-β^2,2-HAc³c-OMe | 254097-86-4

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 肽模拟物
• 英文名称: Boc-β^2,2-HAc³c-β^2,2-HAc³c-β^2,2,-HAc³c-β^2,2,-HAc³c-β^2,2-HAc³c-β^2,2-HAc³c-OMe
• 英文别名: Methyl 1-[[[1-[[[1-[[[1-[[[1-[[[1-[[(2-methylpropan-2-yl)oxycarbonylamino]methyl]cyclopropanecarbonyl]amino]methyl]cyclopropanecarbonyl]amino]methyl]cyclopropanecarbonyl]amino]methyl]cyclopropanecarbonyl]amino]methyl]cyclopropanecarbonyl]amino]methyl]cyclopropane-1-carboxylate；methyl 1-[[[1-[[[1-[[[1-[[[1-[[[1-[[(2-methylpropan-2-yl)oxycarbonylamino]methyl]cyclopropanecarbonyl]amino]methyl]cyclopropanecarbonyl]amino]methyl]cyclopropanecarbonyl]amino]methyl]cyclopropanecarbonyl]amino]methyl]cyclopropanecarbonyl]amino]methyl]cyclopropane-1-carboxylate
• CAS: 254097-86-4
• 化学式: C₃₆H₅₄N₆O₉
• 分子量: 714.86
• InChiKey: IIYMIBBNZDVDAI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.9
• 重原子数：
  51
• 可旋转键数：
  21
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.81
• 拓扑面积：
  210
• 氢给体数：
  6
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  Boc-β^2,2-HAc³c-β^2,2-HAc³c-β^2,2,-HAc³c-β^2,2,-HAc³c-β^2,2-HAc³c-β^2,2-HAc³c-OMe 在 lithium hydroxide 作用下， 以 2,2,2-三氟乙醇 、 水 为溶剂， 反应 6.0h， 以82%的产率得到Boc-β^2,2-HAc³c-β^2,2-HAc³c-β^2,2,-HAc³c-β^2,2,-HAc³c-β^2,2-HAc³c-β^2,2-HAc³c-OH
  参考文献：
  名称：

  Synthesis, Crystal Structures, and Modelling ofβ-Oligopeptides Consisting of 1-(Aminomethyl)cyclopropanecarboxylic Acid: Ribbon-Type Arrangement of Eight-Membered H-Bonded Rings

  摘要：

  Partially and fully protected, and unprotected beta-oligopeptides (3-9) were prepared from 1-(aminomethyl)cyclopropanecarboxylic acid, which, in turn, is readily available from cyanoacetate and dibromoethane. N-Boc and C-OMe protection were applied for the fragment-coupling (1-hydroxy-1H-benzotriazole (HOBt)/1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide hydrochloride (EDC)) solution synthesis. X-Ray crystal structures of the dimer (3), trimer (5), and tetramer (6) are described, and compared with those of the Boc-protected building blocks (2) and of the corresponding trimer (10) consisting of 1-(aminomethyl)cyclohexanecarbonyl residues (cf. Figs. 1 and 2). While the cyclohexane derivative forms ten-membered hydrogen-bonded rings, the characteristic secondary-structural motif in the cyclopropane derivatives is an eight-membered ring with H-bonding between next neighbors (Fig. 1). All cyclopropanecarbonyl moieties in the reported structures have the - generally more stable - s-cis ('bisected') conformation of the C=O groups on the three-membered rings (not preferred with the cyclohexane analog, the exocyclic CO group of which may be in an s-trans, a perpendicular, an axial, or an equatorial position). The bisecting effect and the large exocyclic bond angle (120 degrees) in the cyclopropane units are proposed to provide the 'ordering' elements - on top of the staggering effect of the C(2)-C(3) ethane bond in all beta-peptides - which lead to the observed substituent-induced turn formation. A high degree of intramolecular H-bonding is evident also from IR spectroscopy (Fig. 3), and concentration- and temperature-dependent NMR measurements (Fig. 4) of CHCl3 and CD2Cl2 solutions, indicating that the boat-type arrangement of the eight-membered rings with their unusual H-bonding geometry (Fig. 1, f) is also present in solution. A possible structure of a poly[1-(aminomethyl)cyclopropane-carboxylic acid] consisting of a flight of stairs formed by folded H-bonded eight-membered rings is modelled. using the oligomer X-ray data (Fig. 5). The type of secondary structure found in the solid state of the beta(2.2)-peptides reported here is unprecedented in the realm of alpha-peptides and proteins.

  DOI：

  10.1002/(sici)1522-2675(19991006)82:10<1559::aid-hlca1559>3.0.co;2-a
• 作为产物：
  描述：

  Boc-β^2,2-HAc³c-β^2,2-HAc³c-β^2,2-HAc³c-OMe 在 lithium hydroxide 、 1-羟基苯并三唑 、 1-(3-二甲基氨基丙基)-3-乙基碳二亚胺 、 三乙胺 作用下， 以 甲醇 、 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 86.0h， 生成 Boc-β^2,2-HAc³c-β^2,2-HAc³c-β^2,2,-HAc³c-β^2,2,-HAc³c-β^2,2-HAc³c-β^2,2-HAc³c-OMe
  参考文献：
  名称：

  Synthesis, Crystal Structures, and Modelling ofβ-Oligopeptides Consisting of 1-(Aminomethyl)cyclopropanecarboxylic Acid: Ribbon-Type Arrangement of Eight-Membered H-Bonded Rings

  摘要：

  Partially and fully protected, and unprotected beta-oligopeptides (3-9) were prepared from 1-(aminomethyl)cyclopropanecarboxylic acid, which, in turn, is readily available from cyanoacetate and dibromoethane. N-Boc and C-OMe protection were applied for the fragment-coupling (1-hydroxy-1H-benzotriazole (HOBt)/1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide hydrochloride (EDC)) solution synthesis. X-Ray crystal structures of the dimer (3), trimer (5), and tetramer (6) are described, and compared with those of the Boc-protected building blocks (2) and of the corresponding trimer (10) consisting of 1-(aminomethyl)cyclohexanecarbonyl residues (cf. Figs. 1 and 2). While the cyclohexane derivative forms ten-membered hydrogen-bonded rings, the characteristic secondary-structural motif in the cyclopropane derivatives is an eight-membered ring with H-bonding between next neighbors (Fig. 1). All cyclopropanecarbonyl moieties in the reported structures have the - generally more stable - s-cis ('bisected') conformation of the C=O groups on the three-membered rings (not preferred with the cyclohexane analog, the exocyclic CO group of which may be in an s-trans, a perpendicular, an axial, or an equatorial position). The bisecting effect and the large exocyclic bond angle (120 degrees) in the cyclopropane units are proposed to provide the 'ordering' elements - on top of the staggering effect of the C(2)-C(3) ethane bond in all beta-peptides - which lead to the observed substituent-induced turn formation. A high degree of intramolecular H-bonding is evident also from IR spectroscopy (Fig. 3), and concentration- and temperature-dependent NMR measurements (Fig. 4) of CHCl3 and CD2Cl2 solutions, indicating that the boat-type arrangement of the eight-membered rings with their unusual H-bonding geometry (Fig. 1, f) is also present in solution. A possible structure of a poly[1-(aminomethyl)cyclopropane-carboxylic acid] consisting of a flight of stairs formed by folded H-bonded eight-membered rings is modelled. using the oligomer X-ray data (Fig. 5). The type of secondary structure found in the solid state of the beta(2.2)-peptides reported here is unprecedented in the realm of alpha-peptides and proteins.

  DOI：

  10.1002/(sici)1522-2675(19991006)82:10<1559::aid-hlca1559>3.0.co;2-a

文献信息

• Synthesis, Crystal Structures, and Modelling ofβ-Oligopeptides Consisting of 1-(Aminomethyl)cyclopropanecarboxylic Acid: Ribbon-Type Arrangement of Eight-Membered H-Bonded Rings
  作者：Stefan Abele、Paul Seiler、Dieter Seebach

  DOI：10.1002/(sici)1522-2675(19991006)82:10<1559::aid-hlca1559>3.0.co;2-a

  日期：1999.10.6

  Partially and fully protected, and unprotected beta-oligopeptides (3-9) were prepared from 1-(aminomethyl)cyclopropanecarboxylic acid, which, in turn, is readily available from cyanoacetate and dibromoethane. N-Boc and C-OMe protection were applied for the fragment-coupling (1-hydroxy-1H-benzotriazole (HOBt)/1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide hydrochloride (EDC)) solution synthesis. X-Ray crystal structures of the dimer (3), trimer (5), and tetramer (6) are described, and compared with those of the Boc-protected building blocks (2) and of the corresponding trimer (10) consisting of 1-(aminomethyl)cyclohexanecarbonyl residues (cf. Figs. 1 and 2). While the cyclohexane derivative forms ten-membered hydrogen-bonded rings, the characteristic secondary-structural motif in the cyclopropane derivatives is an eight-membered ring with H-bonding between next neighbors (Fig. 1). All cyclopropanecarbonyl moieties in the reported structures have the - generally more stable - s-cis ('bisected') conformation of the C=O groups on the three-membered rings (not preferred with the cyclohexane analog, the exocyclic CO group of which may be in an s-trans, a perpendicular, an axial, or an equatorial position). The bisecting effect and the large exocyclic bond angle (120 degrees) in the cyclopropane units are proposed to provide the 'ordering' elements - on top of the staggering effect of the C(2)-C(3) ethane bond in all beta-peptides - which lead to the observed substituent-induced turn formation. A high degree of intramolecular H-bonding is evident also from IR spectroscopy (Fig. 3), and concentration- and temperature-dependent NMR measurements (Fig. 4) of CHCl3 and CD2Cl2 solutions, indicating that the boat-type arrangement of the eight-membered rings with their unusual H-bonding geometry (Fig. 1, f) is also present in solution. A possible structure of a poly[1-(aminomethyl)cyclopropane-carboxylic acid] consisting of a flight of stairs formed by folded H-bonded eight-membered rings is modelled. using the oligomer X-ray data (Fig. 5). The type of secondary structure found in the solid state of the beta(2.2)-peptides reported here is unprecedented in the realm of alpha-peptides and proteins.