Z-N^β-Me-L-A2Pr(Boc)-Gly-di-Boc-Spe(4,3) | 138093-86-4

• 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: Z-N^β-Me-L-A2Pr(Boc)-Gly-di-Boc-Spe(4,3)
• 英文别名: N^α-(benzyloxycarbonyl)-N^β-(tert-butoxycarbonyl)-N^β-methyl-L-α,β-diaminopropionylglycyl-N⁵,N⁸-bis(tert-butoxycarbonyl)spermidine；tert-butyl N-methyl-N-[(2S)-3-[[2-[4-[(2-methylpropan-2-yl)oxycarbonyl-[3-[(2-methylpropan-2-yl)oxycarbonylamino]propyl]amino]butylamino]-2-oxoethyl]amino]-3-oxo-2-(phenylmethoxycarbonylamino)propyl]carbamate
• CAS: 138093-86-4
• 化学式: C₃₆H₆₀N₆O₁₀
• 分子量: 736.907
• InChiKey: AOSOAZDKUDOIHX-MHZLTWQESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.31
• 重原子数：
  52.0
• 可旋转键数：
  17.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  193.94
• 氢给体数：
  4.0
• 氢受体数：
  10.0

反应信息

• 作为反应物：
  描述：

  Z-N^β-Me-L-A2Pr(Boc)-Gly-di-Boc-Spe(4,3) 在 palladium 10% on activated carbon 、 氢气 、 N,N-二异丙基乙胺 、 N-[(dimethylamino)-3-oxo-1H-1,2,3-triazolo[4,5-b]pyridin-1-yl-methylene]-N-methylmethanaminium hexafluorophosphate 作用下， 以 甲醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 72.0h， 生成
  参考文献：
  名称：

  蜜蜂病原类芽孢杆菌幼虫类青霉素的全合成及生物学评价

  摘要：

  类青霉素是一组复杂的聚阳离子肽次级代谢产物，具有抗菌和抗真菌活性，由破坏性蜜蜂幼虫病原体类芽孢杆菌幼虫产生，引起致命的幼虫病美洲臭虫病 (AFB)。在此，我们报道了青霉素B2的收敛全合成和结构修正。合成了青霉素 B2 的特定立体异构体，以明确确认天然产物结构并评估生物活性。这些研究揭示了青霉素的 N 末端片段是一种重要的药效基团。使用蜜蜂幼虫和昆虫病原体苏云金芽孢杆菌进行的感染试验表明，青霉霉素在蜜蜂幼虫生态位中击败了细菌竞争对手。最后，我们展示了将青霉素分类为潜在核糖体抑制剂的第一个数据。因此，我们的合成路线是了解P. larvae致病性以及在不久的将来进行彻底的结构-活性-关系以及作用模式研究的又一步。

  DOI：

  10.1021/jacs.1c09616
• 作为产物：
  描述：

  (S)-2-N-Cbz-3-N-Boc-丙酸甲酯 在 三乙基硅烷 、 sodium hydroxide 、 氰基磷酸二乙酯 、 三乙胺 、 三氟乙酸 作用下， 以 四氢呋喃 、 二氯甲烷 、 氯仿 、 N,N-二甲基甲酰胺 为溶剂， 反应 35.33h， 生成 Z-N^β-Me-L-A2Pr(Boc)-Gly-di-Boc-Spe(4,3)
  参考文献：
  名称：

  Total synthesis of galantin I. Acid-catalyzed cyclization of galantinic acid

  摘要：

  The proposed structure of galantin 1, a peptide antibiotic isolated from Bacillus pulvifaciens as a mixture of congeners (1a with the D-ornithine residue and lb with D-lysine; 1a/1b = 9/1), was shown to be incorrect by total synthesis. The substructure 3a, named galantinic acid, was an artifact, and its correct structure was assumed to be the hydroxylated form, 20a or 20b, by spectroscopic comparisons of synthetic la with natural galantin I. The synthesis of both diastereomers, 4a and 4b, again suggested that the sequence of the spermidine moiety of galantin I should be N5,N8. Finally, the correct structure of galantin I as 5a was confirmed by the synthesis of diastereomers 5a and 5b. The synthesis of 5a was accomplished in a convergent manner by the coupling of the protected forms of the constituent amino acids: D-ornithine, 6b, D-alanine, 23b, 11b, 8c, and 19a. Galantinic acid residue 20a, present in natural galantin 1, was found to undergo cyclization with retention of its C3 configuration under the chemical degradation conditions to give the artifact 3a. In order to elucidate the mode of cyclization of 20a to 3a, the synthesis of 20a and its analogues was accomplished in a stereoselective manner from D-serine. The synthesis was characterized by the stereoselective epoxidation of hydroxymethyl (Z)-allylamine 34 and alpha,beta-unsaturated delta-lactone 39. Acidolysis of 20a, 20b, and their analogues suggested that the stereoselective cyclization of galantinic acid was initiated by the formation of delta-lactone 54, which through the sequence of reactions should afford the artifact 3a.

  DOI：

  10.1021/ja00029a031

文献信息

• Total synthesis of galantin I. Revision of the original structure
  作者：Naomi Sakai、Yasufumi Ohfune

  DOI：10.1016/s0040-4039(00)94727-0

  日期：1990.1

  The proposed structure of galantin I, isolated as a mixture of homologs (1a/1b = 9/1), was shown to be incorrect by total synthesis and was revised twice to finally give 5a and 5c, respectively, by total synthesis.

  提出的加兰汀I的建议结构（作为同系物的混合物（1a / 1b = 9/1）分离）在总合成中显示是不正确的，并且经过两次修订以最终在总合成中分别得到5a和5c。