Fmoc-N-ethyl-S-trityl-L-cysteine | 921604-15-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 三苯基化合物
• 英文名称: Fmoc-N-ethyl-S-trityl-L-cysteine
• 英文别名: Fmoc-N-ethyl-S-trityl-cysteine；FMOC-N-ethyl-Cys(Trt)-OH；Fmoc-(Et)Cys(Trt)-OH；(R)-2-[Ethyl-(9H-fluoren-9-ylmethoxycarbonyl)-amino]-3-tritylsulfanyl-propionic acid；(2R)-2-[ethyl(9H-fluoren-9-ylmethoxycarbonyl)amino]-3-tritylsulfanylpropanoic acid
• CAS: 921604-15-1
• 化学式: C₃₉H₃₅NO₄S
• 分子量: 613.777
• InChiKey: JZAVGAGHUMZOQW-BHVANESWSA-N

物化性质

• 沸点：
  753.6±60.0 °C(Predicted)
• 密度：
  1.246±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  8.6
• 重原子数：
  45
• 可旋转键数：
  12
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  92.1
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  Fmoc-N-ethyl-S-trityl-L-cysteine 、 2-chlorotrityl-Ala-H polystyrene resin 在 1-羟基苯并三唑 、 O-(1H-benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate 、 N,N-二异丙基乙胺 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 1.0h， 生成
  参考文献：
  名称：

  Efficient Sequential Segment Coupling Using N-Alkylcysteine-Assisted Thioesterification for Glycopeptide Dendrimer Synthesis

  摘要：

  A highly pure MUC1-derived glycopeptide dendrimer of 22 kDa was prepared by a sequential segment coupling, achieved by an N-alkylcysteine (NAC)-assisted thioesterification. The glycopeptide having C-terminal NAC was prepared by the Fmoc method and converted to the thioester 3-mercaptopgropionic acid treatment. The thioester was condensed with a lysine trimer carrying NAC to afford tetramer, which was then converted to the thioester. Two tetramers were condensed with ethylenediamine to give the octameric glycopeptide dendrimer.

  DOI：

  10.1021/ol801340m
• 作为产物：
  描述：

  S-三苯甲基-L-半胱氨酸 在 氢氧化钾 、 sodium carbonate 作用下， 生成 Fmoc-N-ethyl-S-trityl-L-cysteine
  参考文献：
  名称：

  N-Alkyl cysteine-assisted thioesterification of peptides

  摘要：

  A new method for the preparation of peptide thioester by the post-solid phase peptide synthesis (SPPS) approach was developed. A series of N-alkyl cysteine derivatives were prepared and used as the C-terminus residue of the peptides prepared by the Fmoc SPPS. The synthetic peptides released from resin by TFA were readily converted to the peptide thioester in aqueous 3-mercaptopropionic acid (MPA) without significant side reactions. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2006.11.034
• 作为试剂：
  描述：

  Fmoc-Cys(Me-Pocam)-OH 、 Fmoc-甘氨酸 、 Fmoc-L-缬氨酸 、 Fmoc-L-丙氨酸 、 4-巯基苯基乙酸 、 Fmoc-L-苯丙氨酸 、 FMOC-O-叔丁基-L-丝氨酸 、 Fmoc-O-叔丁基-L-谷氨酸 、 Fmoc-N-三苯甲基-L-天冬酰胺 在 哌啶 、 Fmoc-N-ethyl-S-trityl-L-cysteine 、 rink amide MBHA resin 、 O-(7-azabenzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate 、 乙酸酐 、 1-羟基苯并三唑 、 N,N-二异丙基乙胺 、 N,N'-二环己基碳二亚胺 、 Fmoc-Pbf-L-精氨酸 作用下， 以 N-甲基吡咯烷酮 、 甲醇 、 二氯甲烷 为溶剂， 反应 2.5h， 以2%的产率得到Fmoc-Glu-Asn-Phe-Ser-Gly-Gly-Cys(N-methyl-phenacyloxycarbamidomethyl)-Val-Ala-Gly-(4-SC6H4CH2COOH)
  参考文献：
  名称：

  N-甲基-苯甲酰氧基氨基甲酰氨基（Pocam）基团：用于固相肽合成和肽缩合反应的新型硫醇保护基。

  摘要：

  在用于肽段的缩合的所谓硫酯方法中，化学选择性连接需要氨基和硫醇基的保护基。在这项研究中，我们开发了一种新型的硫醇保护基团，即N-甲基-苯甲酰氧基氨基甲酰氨基甲基（Pocam）。我们将其用于保护半胱氨酸侧链，并合成了含有Pocam的肽和肽硫酯。通过硫酯法将它们冷凝。缩合反应后，通过Zn / AcOH处理裂解Pocam基团。同时，用于保护赖氨酸侧链的叠氮基也被转化为氨基，表明该保护基策略将肽缩合反应后的去保护反应简化为仅一步。

  DOI：

  10.1039/c1ob05253e

文献信息

• Application of a novel thioesterification reaction to the synthesis of chemokine CCL27 by the modified thioester method
  作者：Hironobu Hojo、Yuichi Murasawa、Hidekazu Katayama、Tsuyoshi Ohira、Yuko Nakahara、Yoshiaki Nakahara

  DOI：10.1039/b800884a

  日期：——

  Aryl thioesters of peptide segments were prepared by the conventional 9-fluorenylmethoxycarbonyl (Fmoc) strategy using a novel N-alkyl cysteine (NAC)-assisted thioesterification reaction. The peptide carrying NAC at its C-terminus was prepared by the Fmoc strategy and converted to the aryl thioester by 4-mercaptophenylacetic acid (MPAA) treatment without significant side reactions. The peptide thioester was used for the efficient preparation of 95-amino acid (AA) chemokine CCL27 by an Ag+-free thioester method.

  通过改进的N-烷基半胱氨酸(NAC)辅助硫酯化反应，采用传统的9-芴甲氧羰基(Fmoc)策略制备了肽段的芳基硫酯。含有C端NAC的肽段通过Fmoc策略制备，并通过4-巯基苯乙酸(MPAA)处理转化为芳基硫酯，过程中未发生显著的副反应。这种肽硫酯被用于高效制备95个氨基酸的趋化因子CCL27，采用无Ag+的硫酯方法。
• Improvement of stability of phenacyloxycarbamidomethyl (Pocam) group, a cysteine protecting group removable with zinc reduction, under acidic conditions
  作者：Hidekazu Katayama、Takuma Goto

  DOI：10.1016/j.tetlet.2016.12.081

  日期：2017.2

  In order to improve the stability of phenacyloxycarbamidomethyl (Pocam) group, a cysteine protecting group removable with zinc reduction, under acidic conditions, various alkyl substituents on the nitrogen atom of Pocam group were examined. As a result, attachment of an electron-withdrawing group improved the stability, and 2,2,2-trifluoroethyl (Tfe) group was most effective among four substituents

  为了提高可通过锌还原除去的半胱氨酸保护基苯氧基氧基氨基甲酰甲基（Pocam）基团的稳定性，在酸性条件下，研究了Pocam基团的氮原子上的各种烷基取代基。结果，吸电子基团的连接改善了稳定性，并且在测试的四个取代基中2,2,2-三氟乙基（Tfe）基团最有效。Tfe-Pocam组可用于固相肽合成和肽缩合反应，也可用于区域选择性二硫键形成反应。
• Synthesis of homogeneous MUC1 oligomers via a bi-directional ligation strategy
  作者：Dima Al Sheikha、Brendan L. Wilkinson、Gajan Santhakumar、Morten Thaysen-Andersen、Richard J. Payne

  DOI：10.1039/c3ob41363b

  日期：——

  The efficient synthesis of homogeneous MUC1 peptide oligomers using sequential ligation reactions in the N-to-C and C-to-N directions is reported. The bi-directional ligation strategy makes use of thioester formation via N → S acyl shift chemistry in combination with peptide ligation reactions and was used to prepare a library of peptide oligomers ranging in molecular mass from 3.8–9.4 kDa, comprised

  报道了使用在N到C和C到N方向上的顺序连接反应有效合成均质MUC1肽寡聚体的方法。双向连接策略利用硫酯的形成通过Ñ→S酰基与肽的连接反应组合化学移位，并用来从3.8-9.4 kDa的制备肽的低聚物的测距分子量图书馆，由2和5之间MUC1可变数串联重复序列的重复序列。
• The Mercaptomethyl Group Facilitates an Efficient One-Pot Ligation at Xaa-Ser/Thr for (Glyco)peptide Synthesis
  作者：Hironobu Hojo、Chinatsu Ozawa、Hidekazu Katayama、Akiharu Ueki、Yuko Nakahara、Yoshiaki Nakahara

  DOI：10.1002/anie.201000384

  日期：——

  Going native: A mercaptomethyl group on the side‐chain hydroxy group of serine and threonine residues facilitates a native chemical ligation reaction at the Xaa‐Ser/Thr site (see scheme; R=H or Me). The intermediate thioester is treated to achieve an S‐ to N‐acyl shift. After ligation, the group is spontaneously removed to obtain the glycopeptide contulakin‐G and human calcitonin.

  天然化：丝氨酸和苏氨酸残基的侧链羟基上的巯基甲基有助于Xaa-Ser / Thr位点的天然化学连接反应（请参阅方案； R = H或Me）。中间体硫酯经过处理，可实现S到N酰基的转变。连接后，自发去除该基团以获得糖肽contulakin-G和人降钙素。
• PROCESS FOR PRODUCTION OF PEPTIDE THIOESTER
  申请人：TOKAI UNIVERSITY EDUCATIONAL SYSTEM

  公开号：EP2085403A1

  公开（公告）日：2009-08-05

  An object of the present invention is to provide a method for synthesizing a peptide thioester by using a compound that can be easily obtained within a relatively short time under conditions in which a side reaction is unlikely to occur. In the present invention, a thioester bond is formed by elongating a pepetide chain using N-alkyl cysteine as the C-terminal amino acid according to the Fmoc method, carrying out deprotection, and then causing the peptide bond to undergo N-S transfer to the thiol group of N-alkyl cysteine under weak acidic conditions.

  本发明的目的是提供一种合成肽硫酯的方法，使用一种在较短时间内，在不太可能发生副反应的条件下容易获得的化合物。在本发明中，硫酯键的形成是根据 Fmoc 法，以 N-烷基半胱氨酸作为 C 端氨基酸，拉长肽链，进行脱保护，然后使肽键在弱酸性条件下与 N-烷基半胱氨酸的硫醇基发生 N-S 转移。