Boc-Ser(Al)-Aib-Aib-Ser(Al)-Aib-OMe | 943524-47-8

• 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: Boc-Ser(Al)-Aib-Aib-Ser(Al)-Aib-OMe
• 英文别名: Boc-Ser(Allyl)-Aib-Aib-Ser(Allyl)-Aib-OMe；Boc-Ser(allyl)-Aib-Aib-Ser(allyl)-Aib-OMe；methyl 2-methyl-2-[[(2S)-2-[[2-methyl-2-[[2-methyl-2-[[(2S)-2-[(2-methylpropan-2-yl)oxycarbonylamino]-3-prop-2-enoxypropanoyl]amino]propanoyl]amino]propanoyl]amino]-3-prop-2-enoxypropanoyl]amino]propanoate
• CAS: 943524-47-8
• 化学式: C₃₀H₅₁N₅O₁₀
• 分子量: 641.762
• InChiKey: OFSILORYBZEYEJ-PMACEKPBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  45
• 可旋转键数：
  21
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  200
• 氢给体数：
  5
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  Boc-Ser(Al)-Aib-Aib-Ser(Al)-Aib-OMe 在 RuCl2(1,3-dimesityl-imidazolidin-2-yl)(PCy3)(=CHPh) 、 Hoveyda-Grubbs catalyst second generation 、 双氧水 作用下， 反应 12.0h， 生成
  参考文献：
  名称：

  肽上的 Z-选择性烯烃复分解：侧链影响、预组织和底物选择指南的研究

  摘要：

  烯烃复分解已成为调节生物相关化合物的稳定性和活性的有前途的策略；然而，控制产品中烯烃几何形状的能力仍然是一个挑战。环金属化钌催化剂设计的最新进展催生了实现这种高保真度和Z选择性控制的新策略，但这些催化剂在具有多种功能（包括肽）的基质上的范围和局限性仍有待探索。在此，我们报告了对肽的生产性和非生产性 Z 选择性复分解的各种因素的评估。通过同二聚化、交叉复分解和闭环复分解探索了空间、侧链同一性和通过肽二级结构的预组织的影响。我们的结果表明，氨基酸侧链和烯烃的特性深刻影响环金属化钌催化剂在Z-选择性复分解中的活性。不同肽底物上的交叉复分解和闭环复分解强调了实现高转化率和 Z 选择性的标准。本报告中概述的原理不仅对于扩大 Z-选择性烯烃复分解到肽的范围很重要，而且对于在一般合成工作中应用立体选择性烯烃复分解也很重要。

  DOI：

  10.1021/ja507166g
• 作为产物：
  描述：

  O-烯丙基-N-(叔丁氧羰基)-L-丝氨酸 在 1-羟基苯并三唑 、 盐酸-N-乙基-Nˊ-(3-二甲氨基丙基)碳二亚胺 、 N,N-二异丙基乙胺 、 三氟乙酸 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 190.5h， 生成 Boc-Ser(Al)-Aib-Aib-Ser(Al)-Aib-OMe
  参考文献：
  名称：

  Facile and E-Selective Intramolecular Ring-Closing Metathesis Reactions in 3₁₀-Helical Peptides:  A 3D Structural Study

  摘要：

  The ring-closing metathesis reaction can be used to cross-link allylated serine residues situated at the i and i + 3 positions in 3(10)-helical peptides containing the helicogenic amino acid, alpha-aminoisobutyric acid (Aib). An octapeptide with the sequence Boc-Aib-Aib-Aib-Ser(Al)-Aib-Aib-Ser(Al)-Aib-OMe was found to undergo a facile and > 20:1 E-selective ring-closing metathesis (RCM) reaction catalyzed by the Grubbs second-generation catalyst to yield an 18-membered macrocycle. The formation of this cross-link does not significantly disturb the peptide's native 3(10)-helicity, as judged by an X-ray diffraction study of the acyclic diene, the E-olefin RCM product, and its hydrogenated derivative. A heptapeptide system with the sequence Boc-Val-Ser(Al)-Leu-Aib-Ser(Al)-Val-Leu-OMe also underwent an efficient RCM reaction, albeit with diminished E-selectivity. It is apparent from these studies that a minimal, RCM-derived, macrocyclic constraint can be readily incorporated into 3(10)-helical peptides.

  DOI：

  10.1021/ja071148m

文献信息

• Z-SELECTIVE OLEFIN METATHESIS OF PEPTIDES
  申请人：CALIFORNIA INSTITUTE OF TECHNOLOGY

  公开号：US20160185821A1

  公开（公告）日：2016-06-30

  The invention relates generally to the synthesis of modified amino acids and modified peptides in the presence of cyclometalated catalysts. The invention has utility in the fields of catalysis, organic synthesis, polymer chemistry, and industrial and fine chemicals chemistry.

  该发明通常涉及在环金属催化剂存在下合成改性氨基酸和改性肽。该发明在催化、有机合成、聚合物化学以及工业和精细化学品化学领域具有实用性。
• Z-Selective Olefin Metathesis on Peptides: Investigation of Side-Chain Influence, Preorganization, and Guidelines in Substrate Selection
  作者：Shane L. Mangold、Daniel J. O’Leary、Robert H. Grubbs

  DOI：10.1021/ja507166g

  日期：2014.9.3

  modulating the stability and activity of biologically relevant compounds; however, the ability to control olefin geometry in the product remains a challenge. Recent advances in the design of cyclometalated ruthenium catalysts has led to new strategies for achieving such control with high fidelity and Z selectivity, but the scope and limitations of these catalysts on substrates bearing multiple functionalities

  烯烃复分解已成为调节生物相关化合物的稳定性和活性的有前途的策略；然而，控制产品中烯烃几何形状的能力仍然是一个挑战。环金属化钌催化剂设计的最新进展催生了实现这种高保真度和Z选择性控制的新策略，但这些催化剂在具有多种功能（包括肽）的基质上的范围和局限性仍有待探索。在此，我们报告了对肽的生产性和非生产性 Z 选择性复分解的各种因素的评估。通过同二聚化、交叉复分解和闭环复分解探索了空间、侧链同一性和通过肽二级结构的预组织的影响。我们的结果表明，氨基酸侧链和烯烃的特性深刻影响环金属化钌催化剂在Z-选择性复分解中的活性。不同肽底物上的交叉复分解和闭环复分解强调了实现高转化率和 Z 选择性的标准。本报告中概述的原理不仅对于扩大 Z-选择性烯烃复分解到肽的范围很重要，而且对于在一般合成工作中应用立体选择性烯烃复分解也很重要。
• Facile and <i>E</i>-Selective Intramolecular Ring-Closing Metathesis Reactions in 3₁₀-Helical Peptides:  A 3D Structural Study
  作者：Amie K. Boal、Ivan Guryanov、Alessandro Moretto、Marco Crisma、Erica L. Lanni、Claudio Toniolo、Robert H. Grubbs、Daniel J. O'Leary

  DOI：10.1021/ja071148m

  日期：2007.6.6

  The ring-closing metathesis reaction can be used to cross-link allylated serine residues situated at the i and i + 3 positions in 3(10)-helical peptides containing the helicogenic amino acid, alpha-aminoisobutyric acid (Aib). An octapeptide with the sequence Boc-Aib-Aib-Aib-Ser(Al)-Aib-Aib-Ser(Al)-Aib-OMe was found to undergo a facile and > 20:1 E-selective ring-closing metathesis (RCM) reaction catalyzed by the Grubbs second-generation catalyst to yield an 18-membered macrocycle. The formation of this cross-link does not significantly disturb the peptide's native 3(10)-helicity, as judged by an X-ray diffraction study of the acyclic diene, the E-olefin RCM product, and its hydrogenated derivative. A heptapeptide system with the sequence Boc-Val-Ser(Al)-Leu-Aib-Ser(Al)-Val-Leu-OMe also underwent an efficient RCM reaction, albeit with diminished E-selectivity. It is apparent from these studies that a minimal, RCM-derived, macrocyclic constraint can be readily incorporated into 3(10)-helical peptides.