(2S,5S,8S,11S)-1-Acetyl-1,4-diaza-3-keto-5-carboxy-10-thiatricyclo<2.8.1.0^4,8>tridecane | 120980-87-2

• 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: (2S,5S,8S,11S)-1-Acetyl-1,4-diaza-3-keto-5-carboxy-10-thiatricyclo<2.8.1.0^4,8>tridecane
• 英文别名: Ac-Hel₁-OH；Ac-Hel1-OH；(2S,5S,8S,11S)-1-Acetyl-1,4-diaza-3-keto-5-carboxy-10-thiatricyclo[2.8.1.0^4,8]tridecane；(1S,4S,7S,10S)-12-acetyl-2-oxo-9-thia-3,12-diazatricyclo[8.2.1.03,7]tridecane-4-carboxylic acid
• CAS: 120980-87-2
• 化学式: C₁₃H₁₈N₂O₄S
• 分子量: 298.363
• InChiKey: GDJDYAZQPWCIEB-NAKRPEOUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.1
• 重原子数：
  20
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.77
• 拓扑面积：
  103
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (2S,5S,8S,11S)-1-Acetyl-1,4-diaza-3-keto-5-carboxy-10-thiatricyclo<2.8.1.0^4,8>tridecane 在 4-二甲氨基吡啶 、 sodium hydroxide 、 N,N'-羰基二咪唑 作用下， 以 吡啶 为溶剂， 反应 9.0h， 生成 Ac-Hel1-L-Lac-OH
  参考文献：
  名称：

  Kemp; Allen; Oslick, Journal of the American Chemical Society, 1995, vol. 117, # 25, p. 6641 - 6646

  摘要：

  DOI：
• 作为产物：
  描述：

  (3R,5S)-5-(methoxycarbonyl)-1-acetylpyrrolidin-3-yl 4-methylbenzenesulfonate 在 4-二甲氨基吡啶 吡啶 、 sodium hydroxide 、 氨 、 sodium 、 N,N'-二环己基碳二亚胺 、 三氟乙酸 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 甲醇 、 二氯甲烷 、 水 、 二甲基亚砜 、 乙酸乙酯 为溶剂， 反应 47.17h， 生成 (2S,5S,8S,11S)-1-Acetyl-1,4-diaza-3-keto-5-carboxy-10-thiatricyclo<2.8.1.0^4,8>tridecane
  参考文献：
  名称：

  Studies of N-terminal templates for .alpha.-helix formation. Synthesis and conformational analysis of (2S,5S,8S,11S)-1-acetyl-1,4-diaza-3-keto-5-carboxy-10-thiatricyclo[2.8.1.04,8]tridecane (Ac-Hel1-OH)

  摘要：

  A convergent synthesis of the title compound, a conformationally restricted analogue of acetyl-L-prolyl-L-proline, from 1-acetyl-2(S)-carboxy-4(S)-mercaptopyrrolidine and trans-1-(tert-butoxycarbonyl)-2(S)-(methoxy-carbonyl)-5(S)-[(tosyloxy)methyl]pyrrolidine (Ac-Hel1-OH) is reported, along with a synthesis of (2S,8S,11S)-1-acetyl-1,4-diaza-3-keto-10-thiatricyclo[2.8.0(4,8)]tridecane. In the crystal and in CDCl3 solution the conformation of Ac-Hel1-OH is shown to approximate a staggered orientation at the 8,9-CC bond and an s-cis orientation at the acetyl amide bond. In DMF, DMSO, MeCN, and D2O significant amounts of the s-trans conformer are also present.

  DOI：

  10.1021/jo00023a037

文献信息

• Optimal N-Caps for N-Terminal Helical Templates:  Effects of Changes in H-Bonding Efficiency and Charge
  作者：Wolfgang Maison、Eva Arce、Peter Renold、Robert J. Kennedy、Daniel S. Kemp

  DOI：10.1021/ja010812a

  日期：2001.10.1

  formation. Replacement of the N-acetyl by urethane, urea, or sulfonamide generated less efficient polypeptide helix inducers. The N-formyl cap is found to be equivalent to the N-acetyl and may provide more convenient quantitative helix reporting properties. Anionic N-caps derived from the series X = (-)O(2)C-(CH(2))(n)-CO, 0 < or = n < or = 3, are superior to N-acetyl, as are N-acylglycyl and N-acyl-beta-aspartyl

  引入了一系列有效的螺旋起始 N 端帽 X-Hel，扩展了先前报告的构象模板 Ac-Hel 的范围和多功能性，（Kemp, DS; Allen, TJ; Oslick, SJ Am. Chem. Soc . 1995, 117, 6641-6657) 并且描述了基于结构特异性分子内氢键形成预测帽盖性能的工作原理。用氨基甲酸乙酯、尿素或磺酰胺替代 N-乙酰基会产生效率较低的多肽螺旋诱导剂。发现 N-甲酰基帽等同于 N-乙酰基，可以提供更方便的定量螺旋报告特性。衍生自系列 X = (-)O(2)C-(CH(2))(n)-CO, 0 < 或 = n < 或 = 3 的阴离子 N-帽优于 N-乙酰基，正如N-酰基甘氨酰和 N-酰基-β-天冬氨酰。后一对帽允许在多肽链内引入 X-Hel 功能，从而控制肽子序列的螺旋度。讨论了这些上限函数的应用。这项工作主要侧重于直接的实际目标，旨在提高水溶液中分离的中
• (2S,5S,8S,11S)-1-Acetyl-1,4-diaza-3-keto-5-carboxy-10-thia-tricyclo-[2.8.04,8]-tridecane, 1 synthesis of prolyl-proline-derived, peptide-functionalized templates for α-helix formation
  作者：D.S. Kemp、Timothy P. Curran

  DOI：10.1016/s0040-4039(00)80644-9

  日期：1988.1
• Studies of N-terminal templates for .alpha.-helix formation. Synthesis and conformational analysis of peptide conjugates of (2S,5S,8S,11S)-1-acetyl-1,4-diaza-3-keto-5-carboxy-10-thiatricyclo[2.8.1.04,8]tridecane (Ac-Hel1-OH)
  作者：D. S. Kemp、Timothy P. Curran、James G. Boyd、Thomas J. Allen

  DOI：10.1021/jo00023a038

  日期：1991.11

  The following peptide conjugates of the above-named template molecule were prepared: Ac-Hel1-(L-Ala)n-OtBu (n = 1-6) and Ac-Hel1-Sar-(L-Ala)n-OtBu (n = 1-4), where Sar = N-methylglycine. The slowly equilibrating acetamido function causes the H-1 NMR spectrum in CDCl3, CD3CN, DMF-d7, and DMSO-d6 to be split into pairs of resonances corresponding to the s-cis (c) and s-trans (t) amide conformations. The (t)/(c) ratio is formed to be length and solvent dependent for the homoAla oligomers, and the pattern of resonances in the delta-2-3 region of these conjugates is shown to be consistent with a change in conformation at the C-8-C-9 bond concurrent with length-dependent (t) state formation. Study of NOE properties, temperature and solvent dependences of NH chemical shifts, and J-alpha-CH-NH values are shown to be consistent with an assignment of random coil conformations for the (c) states and template-nucleated helical conformations for the (t) states. Solvent-dependent helicity propagation parameters are assigned.
• KEMP, D. S.;CURRAN, TIMOTHY P., TETRAHEDRON LETT., 29,(1988) N 39, C. 4931-4934
  作者：KEMP, D. S.、CURRAN, TIMOTHY P.

  DOI：——

  日期：——