5-(tert-butyl) 1-methyl (tert-butoxycarbonyl)-L-glutamate | 18635-51-3

• 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: 5-(tert-butyl) 1-methyl (tert-butoxycarbonyl)-L-glutamate
• 英文别名: N-Boc-Glu(Ot-Bu)OCH₃；Boc-L-Glu(O-t-Bu)-OMe；Boc-Glu(OtBu)-OMe；(S)-5-tert-Butyl 1-methyl 2-((tert-butoxycarbonyl)amino)pentanedioate；5-O-tert-butyl 1-O-methyl (2S)-2-[(2-methylpropan-2-yl)oxycarbonylamino]pentanedioate
• CAS: 18635-51-3
• 化学式: C₁₅H₂₇NO₆
• 分子量: 317.382
• InChiKey: QJMOKJOSDZAYSQ-JTQLQIEISA-N

物化性质

• 沸点：
  403.1±35.0 °C(Predicted)
• 密度：
  1.072±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  22
• 可旋转键数：
  10
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  90.9
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  5-(tert-butyl) 1-methyl (tert-butoxycarbonyl)-L-glutamate 在 sodium tetrahydroborate 、 lithium chloride 作用下， 以 四氢呋喃 、 乙醇 为溶剂， 以93%的产率得到tert-butyl 4(S)-(tert-butoxycarbonylamino)-5-hydroxypentanoate
  参考文献：
  名称：

  Investigation of the Active Site of Aminopeptidase A Using a Series of New Thiol-Containing Inhibitors

  摘要：

  Aminopeptidase A (APA) and aminopeptidase N (APN) are two metallopeptidases which have been suggested to be involved in the enzymatic cascade of the renin-angiotensin system. APA liberates angotensin III from angiotensin II by releasing the N-terminal aspartate, and APN participates in the inactivation of angiotensin III. As the role of angiotensin III in the regulation of blood pressure in the central nervous system and at the periphery is controversial, it was of interest to develop selective and efficient inhibitors of APA. Starting from Glu-thiol,(1) which was the first efficient APA inhibitor described, but however is equipotent on APA (K-i = 0.14 mu M) and APN (K-i = 0.12 mu M), beta-amino thiols bearing various carboxyalkyl chains have been synthesized and their inhibitory potencies measured on both purified enzymes. Compounds containing a carboxylated aromatic ring inhibited APA and APN with K-i values in the micromolar range but were slightly more active on APA. Conversely, inhibitors containing a cyclohexyl ring were more efficient on APN. Various modifications of the structure of Glu-thiol decreased inhibitory activity on both enzymes but increased the selectivity for APA, and compound 9d ((S)-4-amino-6-mercaptohexanoic acid) was 23 times more potent on APA (K-i = 2.0 mu M) than on APN (K-i = 45 mu M).

  DOI：

  10.1021/jm00035a014
• 作为产物：
  描述：

  二碳酸二叔丁酯 、 OtBu-L-谷氨酸甲酯盐酸盐 在 三乙胺 作用下， 以 二氯甲烷 为溶剂， 以90%的产率得到5-(tert-butyl) 1-methyl (tert-butoxycarbonyl)-L-glutamate
  参考文献：
  名称：

  用于肽合成的底物导向路易斯酸催化

  摘要：

  一种路易斯酸催化的底物定向形成肽键的方法已经被开发出来，这种强大的方法被用于在无溶剂条件下对羧基进行新的“远程”活化。该方法具有以下优点：1）高产肽合成对任何氨基酸均使用钽催化剂；2) 反应进行时没有任何外消旋化；3）采用钛催化剂的新型底物导向化学连接适用于会聚肽合成。这些优势克服了经典肽合成中一些未解决的问题。

  DOI：

  10.1021/jacs.9b03850

文献信息

• A strategy for generating alkyl radicals from aliphatic esters and lactones via sequential hydrolysis and photoinduced decarboxylation
  作者：Hikaru Saito、Takayuki Kanetake、Kazuyuki Osaka、Kousuke Maeda、Toshio Morita、Yasuharu Yoshimi

  DOI：10.1016/j.tetlet.2015.02.020

  日期：2015.3

  photoinduced decarboxylation of methyl aliphatic esters lead to efficient generation of alkyl radicals under mild conditions. The generated alkyl radicals react with a variety of reagents to produce addition, reduction, and substitution products. In addition, the new tin and halogen free process for alkyl radical generation is applicable to a variety of aliphatic esters including those of dipeptides, steroids

  甲基脂族酯的顺序水解和光诱导的脱羧作用导致在温和条件下有效生成烷基。生成的烷基与多种试剂反应，生成加成，还原和取代产物。另外，用于产生烷基自由基的新的无锡和卤素的方法适用于多种脂族酯，包括二肽，类固醇，糖和内酯。
• Synthesis of β-ketophosphonate analogs of glutamyl and glutaminyl adenylate, and selective inhibition of the corresponding bacterial aminoacyl-tRNA synthetases
  作者：Christian Balg、Sébastien P. Blais、Stéphane Bernier、Jonathan L. Huot、Manon Couture、Jacques Lapointe、Robert Chênevert

  DOI：10.1016/j.bmc.2006.09.056

  日期：2007.1.1

  Escherichia coli glutamyl-tRNA synthetase (GluRS) with a K(i) of 18microM with respect to its substrate glutamate, and binds at one site on this monomeric enzyme; the non-cognate Gln-KPA also binds this GluRS at one site, but is a much weaker (K(i)=2.9mM) competitive inhibitor. By contrast, Gln-KPA inhibits E. coli glutaminyl-tRNA synthetase (GlnRS) by binding competitively but weakly at two distinct sites

  氨酰基-β-酮膦酸酯-腺苷（aa-KPA）是氨酰基腺苷酸酯的稳定类似物，它们是通过氨酰基-tRNA合成酶（aaRS）催化形成氨酰基-tRNA的高能中间体。我们已经合成了谷氨酰-β-酮膦酸酯-腺苷（Glu-KPA）和谷氨酰胺-β-酮膦酸酯-腺苷（Gln-KPA），并测试了它们作为其同源aRS和非同源aRS的抑制剂。Glu-KPA是大肠杆菌谷氨酰tRNA合成酶（GluRS）的竞争性抑制剂，相对于其底物谷氨酸，K（i）为18microM，并在该单体酶的一个位点结合。非同源的Gln-KPA也可以在一个位点结合该GluRS，但竞争性抑制剂（K（i）= 2.9mM）弱得多。相比之下，Gln-KPA抑制E。大肠杆菌谷氨酰胺基-tRNA合成酶（GlnRS），通过竞争性结合但在该酶的两个不同位点弱结合（平均K（i）为0.65mM）；非同源Glu-KPA显示出对GlnRS的一处弱竞争性抑制（K（i）= 2.8
• Kinetic Selection in the Out‐of‐Equilibrium Autocatalytic Reaction Networks that Produce Macrocyclic Peptides
  作者：Xiaoming Miao、Arpita Paikar、Benjamin Lerner、Yael Diskin‐Posner、Guy Shmul、Sergey N. Semenov

  DOI：10.1002/anie.202105790

  日期：2021.9.6

  Autocatalytic reaction networks are instrumental for validating scenarios for the emergence of life on Earth and for synthesizing life de novo. Here, we demonstrate that dimeric thioesters of tripeptides with the general structure (Cys-Xxx-Gly-SEt)2 form strongly interconnected autocatalytic reaction networks that predominantly generate macrocyclic peptides up to 69 amino acids long. Some macrocycles

  自催化反应网络有助于验证地球上生命出现的情景和从头合成生命。在这里，我们证明了三肽的二聚硫酯具有一般结构 (Cys-Xxx-Gly-SEt) 2形成强烈互连的自催化反应网络，主要生成长达 69 个氨基酸的大环肽。从产物池中分离出一些 6-12 个氨基酸的大环，并通过 NMR 光谱和单晶 X 射线分析进行表征。我们研究了丙烯酰胺存在下流动反应器中大环的自催化形成，丙烯酰胺与硫醇的共轭加成作为模型“去除”反应。这些结果表明，即使不是模板辅助的自催化生产与开放隔室中分子种类的竞争去除相结合，也可能是在分子进化的前达尔文阶段选择功能分子的可行途径。
• Sodium methoxide: a simple but highly efficient catalyst for the direct amidation of esters
  作者：Takashi Ohshima、Yukiko Hayashi、Kazushi Agura、Yuka Fujii、Asako Yoshiyama、Kazushi Mashima

  DOI：10.1039/c2cc32153j

  日期：——

  A simple NaOMe catalyst provides superior accessibility to a wide variety of functionalized amides including peptides through direct amination of esters in an atom-economical and environmentally benign way.

  使用简单的 NaOMe 催化剂，就能以原子经济、对环境无害的方式，通过酯的直接胺化，获得包括肽在内的各种官能化酰胺。
• Schroeder,E.; Klieger,E., Justus Liebigs Annalen der Chemie, 1964, vol. 673, p. 196 - 207
  作者：Schroeder,E.、Klieger,E.

  DOI：——

  日期：——