Boc-Leu-SH | 137169-45-0

• 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-Leu-SH
• 英文别名: BocLeuSH；N^α-Boc-Leu-SH；(2S)-4-methyl-2-[(2-methylpropan-2-yl)oxycarbonylamino]pentanethioic S-acid
• CAS: 137169-45-0
• 化学式: C₁₁H₂₁NO₃S
• 分子量: 247.359
• InChiKey: VGDKXFXZPZHZHP-QMMMGPOBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  16
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  56.4
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  Boc-Leu-SH 在 ammonium hydroxide 、 sodium dihydrogenphosphate 、 三异丙基硅烷 、 异氰酸叔丁酯 、 氨 、 水 、 三(2-羰基乙基)磷盐酸盐 、 1-羟基苯并三唑 、 溶剂黄146 、 三氟乙酸 、 苯酚 作用下， 以 甲醇 、 氯仿 、 水 为溶剂， 反应 33.5h， 生成 缩宫素
  参考文献：
  名称：

  Revisiting Oxytocin through the Medium of Isonitriles

  摘要：

  The reaction of thioamino acids and N-terminal peptides, mediated by hindered isonitriles and hydroxybenzotriazole, gives rise to peptide bonds. In one pathway, oxytocin was synthesized by eight such reiterative amidations. In another stereospecific track, oxytocin was constructed by native chemical ligation, wherein the two building blocks were assembled by thioacid amine amidation. The NMR spectra of oxytocin and dihydrooxytocin suggest a high level of preorganization in the latter, perhaps favoring oxidative folding.

  DOI：

  10.1021/ja3063452
• 作为产物：
  描述：

  ethoxycarbonyl (2S)-4-methyl-2-[(2-methylpropan-2-yl)oxycarbonylamino]pentanoate 在 sodium hydrogensulfide 作用下， 反应 0.5h， 生成 Boc-Leu-SH
  参考文献：
  名称：

  Synthesis of Chiral 3,4,5,6-Tetrahydro-1,4-thiazin-2-ones (Thiamorpholin-2-ones) - Novel Heterocycles Possessing Enhanced Carbonyl Electrophilicity over their Oxygen Counterparts

  摘要：

  我们在此报道了首个具有1,4-噻嗪酮核心的手性衍生物的合成。正如预测的那样，硫内酯比等效的内酯系统更易于受到亲核攻击。

  DOI：

  10.1055/s-2006-951548

文献信息

• Facile N-Urethane-Protected α-Amino/Peptide Thioacid Preparation Using EDC and Na2S
  作者：Vommina Sureshbabu、T. Vishwanatha、M. Samarasimhareddy

  DOI：10.1055/s-0031-1290091

  日期：2012.1

  We report herein an efficient protocol for the synthesis of N-urethane-protected α-amino/peptide thioacids from their corresponding acids mediated by EDC and Na2S. The fast reaction under mild conditions enabled the process to be completed in shorter duration with good yield circumventing column purification. The chemistry is compatible with a wide variety of urethane protecting groups, side-chain functionalities, and sterically hindered amino ­acids.

  本文报道了一种高效的方法，通过EDC和Na2S介导，从相应的酸合成N-urethane保护的α-氨基酸/肽硫酸酯。在温和条件下快速反应使得该过程能在较短时间内完成，且产率良好，无需柱层析纯化。该化学方法适用于多种urethane保护基团、侧链功能团以及空间位阻氨基酸。
• An alternate preparation of thioester resin linkers for solid-phase synthesis of peptide C-terminal thioacids
  作者：Alex S Goldstein、Michael H Gelb

  DOI：10.1016/s0040-4039(00)00266-5

  日期：2000.4

  An alternative preparation of thioester resin linkers for solid-phase synthesis of peptide C-terminal thioacids is presented.

  提供了用于肽C-末端硫代酸的固相合成的硫代酯树脂接头的另一种制备方法。
• Peptide Thioacylation with High Stereochemical Preservation
  作者：Thomas Hoeg-Jensen、Arne Holm、Hilmer Sorensen

  DOI：10.1055/s-1996-4437

  日期：1996.3

  A dipeptide thioamide model system, Boc-Leu-ψ[CSNH]-MetOMe, was used for evaluating the preservation of amino acid stereochemistry during thioacylation utilizing amino monothio acids. The LL and DL peptide diastereomers were separated by use of high performance capillary electrophoresis (micellar electrokinetic capillary chromatography). The described thioacylation method combines monothio acids with coupling reagents of the PyBOP-family for generating active thiono esters with low-levels of enantiomerisation (<2%). The best results in terms of stereochemical preservation and yield were obtained with PyNOP, a 6-nitro analog of PyBOP. The successful activation of thiobenzoic acid with all four coupling reagents extended the scope of the method to include aryl monothio acids.

  利用二肽硫代酰胺模型体系 Boc-Leu-Ï[CSNH]-MetOMe 评估了利用氨基单硫酸进行硫代酰化时氨基酸立体化学的保留情况。利用高效毛细管电泳（胶束电动毛细管色谱法）对 LL 和 DL 肽非对映异构体进行了分离。所述硫代酰化方法将单硫代酸与 PyBOP 家族的偶联试剂结合在一起，可生成对映体化程度较低（<2%）的活性硫代酯。使用 PyBOP 的 6-硝基类似物 PyNOP 可获得最佳的立体化学保存效果和产率。用所有四种偶联试剂成功活化了硫代苯甲酸，从而将该方法的应用范围扩展到了芳基一硫代酸。
• Total Synthesis of Cyclosporine: Access to N-Methylated Peptides via Isonitrile Coupling Reactions
  作者：Xiangyang Wu、Jennifer L. Stockdill、Ping Wang、Samuel J. Danishefsky

  DOI：10.1021/ja100517v

  日期：2010.3.31

  tertiary amide bond formations have been applied to a novel total synthesis of the important cyclic polypeptide cyclosporine A. Specifically, the disclosed synthetic route demonstrates the utility of microwave-mediated carboxylic acid isonitrile couplings, thioacid isonitrile couplings at ambient temperature, and isonitrile-mediated couplings of carboxylic acids and thioacids with amines to form challenging

  使用异腈提供仲和叔酰胺键形成的最新进展已应用于重要环状多肽环孢菌素 A 的新型全合成。 具体而言，所公开的合成路线证明了微波介导的羧酸异腈偶联、硫代酸的效用环境温度下的异腈偶联，以及异腈介导的羧酸和硫代酸与胺的偶联以形成具有挑战性的酰胺键。
• Synthesis of Endothiopeptides and Their Cyclization to 1,3-Thiazol-5(4H)-imines
  作者：Jürg Lehmann、Heinz Heimgartner

  DOI：10.1002/(sici)1522-2675(19991110)82:11<1899::aid-hlca1899>3.0.co;2-m

  日期：1999.11.10

  Further investigations of the synthesis of endothio analogues of the segment 1-10 (8) of an apolar analogon of zervamicin IIA are described. The endothiodecapeptide Boc-Trp-Ile-Ala-Aib-Ile-Val-Aib-Leu-Aib-Psi(CS)-Pro-OMe (10) has been prepared in good yield by our novel methodology. On the other hand, all attempts to prepare endothio analogues of 8 with the thioamide group at position 3 (Ala') gave not the expected linear endothiopeptides but led to epimerized 1,3-thiazol-5(4H)-imine derivatives as the main products. The mixture of epimers of the thiazolimines 27, 30, and 31 have been separated by means of preparative HPLC, and their structures have been established by 2D-NMR experiments.