S-phenyl 2-((tert-butoxycarbonyl)amino)-4-methylpentanethioate | 55226-89-6

• 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: S-phenyl 2-((tert-butoxycarbonyl)amino)-4-methylpentanethioate
• 英文别名: Boc-Leu-SPh；S-phenyl (2S)-4-methyl-2-[(2-methylpropan-2-yl)oxycarbonylamino]pentanethioate
• CAS: 55226-89-6
• 化学式: C₁₇H₂₅NO₃S
• 分子量: 323.456
• InChiKey: BJCKACDAUQAFLS-AWEZNQCLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.24
• 重原子数：
  22.0
• 可旋转键数：
  5.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  55.4
• 氢给体数：
  1.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  S-phenyl 2-((tert-butoxycarbonyl)amino)-4-methylpentanethioate 在 盐酸 作用下， 以 1,4-二氧六环 为溶剂， 反应 0.75h， 生成 H-Leu-SPh
  参考文献：
  名称：

  Total Synthesis of Human Galanin-Like Peptide through an Aspartic Acid Ligation

  摘要：

  Human galanin-like peptide (hGALP) is a newly discovered hypothalamic peptide that plays important roles in the regulation of food intake and energy balance. Here, we demonstrate that the aspartic acid ligation can be employed to achieve an efficient synthesis of hGALP. The total synthesis of hGALP enhances our ability to study its biology and facilitates the development of more stable analogues.

  DOI：

  10.1021/ol402984r
• 作为产物：
  描述：

  二碳酸二叔丁酯 在 1-羟基苯并三唑 、 sodium hydroxide 作用下， 以 1,4-二氧六环 、 水 、 乙酸乙酯 为溶剂， 反应 6.08h， 生成 S-phenyl 2-((tert-butoxycarbonyl)amino)-4-methylpentanethioate
  参考文献：
  名称：

  基于α-芳基和α-烷基异氰基（硫代）乙酸酯与乙烯基酮的两步式[3 + 2]环加成反应，季铵化Δ4-和Δ5-脱氢脯氨酸的对映选择性合成

  摘要：

  光学活性的季Δ的发散合成4 -和Δ 5 -脱氢脯氨酸是基于制定了关于第一催化对映选择性共轭加成的α取代的异（硫代）乙酸盐以乙烯基酮是一般两个α -芳基和α -烷基异氰基（硫代）乙酸盐。由于双官能叔胺/方胺催化剂的存在，不需要任何金属盐就可以形成新的四取代的C-N立体中心，它具有庞大的聚芳基侧链和固态时方胺间的距离非常短。

  DOI：

  10.1002/chem.201703526

文献信息

• Visible Light-Induced Trifluoromethylation and Perfluoroalkylation of Cysteine Residues in Batch and Continuous Flow
  作者：Cecilia Bottecchia、Xiao-Jing Wei、Koen P. L. Kuijpers、Volker Hessel、Timothy Noël

  DOI：10.1021/acs.joc.6b01031

  日期：2016.8.19

  We report a visible light-induced trifluoromethylation and perfluoroalkylation for cysteine conjugation using Ru(bpy)32+ as photocatalyst and inexpensive RFI as coupling partner. The protocol allows the introduction of a variety of perfluoro alkyl groups (C1–C10) and a CF2COOEt moiety. The reaction is high yielding (56–94% yield) and fast (2 h in batch, 12 examples). Process intensification in a photomicroreactor

  我们报告可见光诱导的三氟甲基化和全氟烷基化的半胱氨酸偶联使用Ru（bpy）3 2+作为光催化剂和廉价的R F I作为偶联伙伴。该协议允许引入各种全氟烷基（C1-C10）和CF 2 COOEt部分。该反应收率高（56-94％），速度快（分批2 h，12个实例）。在光微反应器中的过程强化加速了反应（5分钟反应时间）并增加了产率（8个实施例）。量子产率研究支持自由基链机制。
• Visible‐Light‐Mediated Selective Arylation of Cysteine in Batch and Flow
  作者：Cecilia Bottecchia、Maarten Rubens、Smita B. Gunnoo、Volker Hessel、Annemieke Madder、Timothy Noël

  DOI：10.1002/anie.201706700

  日期：2017.10.2

  Chemical modifications of peptides: The mild visible-light-mediated arylation of cysteine relies on the use of eosin Y as a metal-free photocatalyst and aryldiazonium salts as arylating agents. The batch and flow protocol afforded a series of arylated cysteine derivatives and arylated cysteine-containing dipeptides. A model peptide has been chemoselectively arylated under biocompatible reaction conditions

  肽的化学修饰：半胱氨酸的温和可见光介导的芳基化依赖于曙红Y作为无金属的光催化剂和芳基重氮盐作为芳基化剂的使用。分批和流动方案提供了一系列芳基化的半胱氨酸衍生物和含芳基化的半胱氨酸的二肽。模型肽已在生物相容性反应条件下化学选择性芳基化。
• Application of dehydroalanine as a building block for the synthesis of selenocysteine-containing peptides
  作者：Kishorkumar M. Reddy、Govindasamy Mugesh

  DOI：10.1039/c8ra09880h

  日期：——

  the interesting redox properties of the selenium atom in peptides and proteins play crucial roles in redox catalysis. However, the chemical synthesis of Sec-containing peptides has been a difficult task. In this paper, we report on a new method for the synthesis of Sec and Sec-containing peptides using dehydroalanine (Dha) as a building block.

  硒代半胱氨酸 (Sec) 是第 21种蛋白质氨基酸，共翻译插入到许多天然蛋白质中。它由双重功能终止密码子 UGA（蛋白石）编码。它是一种氧化还原活性氨基酸，存在于几种参与氧化还原反应的酶的活性位点。这些酶包括三种主要的哺乳动物硒蛋白谷胱甘肽过氧化物酶 (GPx)、硫氧还蛋白还原酶 (TrxR) 和碘甲状腺原氨酸脱碘酶 (Dio)。虽然 Sec 在结构上与其硫类似物半胱氨酸 (Cys) 相似，但较低的 p K a与 Cys 相比，Sec 中的硒醇基团和肽和蛋白质中硒原子的有趣氧化还原特性在氧化还原催化中起着至关重要的作用。然而，含 Sec 肽的化学合成一直是一项艰巨的任务。在本文中，我们报告了一种使用脱氢丙氨酸 (Dha) 作为构建块合成 Sec 和含 Sec 肽的新方法。
• Fully Synthetic Granulocyte Colony-Stimulating Factor Enabled by Isonitrile-Mediated Coupling of Large, Side-Chain-Unprotected Peptides
  作者：Andrew G. Roberts、Eric V. Johnston、Jae-Hung Shieh、Joseph P. Sondey、Ronald C. Hendrickson、Malcolm A. S. Moore、Samuel J. Danishefsky

  DOI：10.1021/jacs.5b08754

  日期：2015.10.14

  Human granulocyte colony-stimulating factor (G-CSF) is an endogenous glycoprotein involved in hematopoiesis. Natively glycosylated and nonglycosylated recombinant forms, lenograstim and filgrastim, respectively, are used clinically to manage neutropenia in patients undergoing chemotherapeutic treatment. Despite their comparable therapeutic potential, the purpose of O-linked glycosylation at Thr133 remains a subject of controversy. In light of this, we have developed a synthetic platform to prepare G-CSF aglycone with the goal of enabling access to native and designed glycoforms with site-selectivity and glycan homogeneity. To address the synthesis of a relatively large, aggregation-prone sequence, we advanced an isonitrile-mediated ligation method. The chemoselective activation and coupling of C-terminal peptidyl Gly thio acids with the N-terminus of an unprotected peptide provide ligated peptides directly in a manner complementary to that with conventional native chemical ligation-desulfurization strategies. Herein, we describe the details and application of this method as it enabled the convergent total synthesis of G-CSF aglycone.