L-gulose hyroxylamine | 1226812-51-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: L-gulose hyroxylamine
• 英文别名: N-[(3aS,4S,6R,6aS)-6-[(4S)-2,2-dimethyl-1,3-dioxolan-4-yl]-2,2-dimethyl-3a,4,6,6a-tetrahydrofuro[3,4-d][1,3]dioxol-4-yl]hydroxylamine
• CAS: 1226812-51-6
• 化学式: C₁₂H₂₁NO₆
• 分子量: 275.302
• InChiKey: FLWZKKRGBHCGBS-SVSWQMSJSA-N

物化性质

• 沸点：
  383.0±52.0 °C(Predicted)
• 密度：
  1.30±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -0.3
• 重原子数：
  19
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  78.4
• 氢给体数：
  2
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  L-gulose hyroxylamine 在 magnesium sulfate 、 zinc(II) chloride 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 9.5h， 生成 (R)-4,4-dichloro-2-((3aS,4S,6R,6aR)-6-((S)-2,2-dimethyl-1,3-dioxolan-4-yl)-2,2-dimethyltetrahydrofuro[3,4-d][1,3]dioxol-4-yl)-3-isopropylisoxazolidin-5-one
  参考文献：
  名称：

  α,α-Dichloroisoxazolidinones for the Synthesis and Chemoselective Peptide Ligation of α-Peptide α-Ketoacids

  摘要：

  In seeking to develop an iterative approach to the preparation of alpha-oligopeptides by the chemoselective amide-forming coupling of alpha-ketoacids and hydroxylamines, we have designed and synthesized novel enantiopure monomers. Key to our approach is the use of alpha,alpha-dichloroacids as masked alpha-ketoacids. The preparation of these monomers, their coupling with alpha-ketoacids, and the conversion of the alpha,alpha-dichloroacids to alpha-ketoacids is described. These studies provide a first step to a conceptually unique approach to peptide synthesis that does not require activating reagents or produce chemical byproducts.

  DOI：

  10.3987/com-10-s(e)106

文献信息

• Aspartic Acid Forming α-Ketoacid–Hydroxylamine (KAHA) Ligations with (<i>S</i>)-4,4-Difluoro-5-oxaproline
  作者：Simon Baldauf、Ayodele O. Ogunkoya、Gábor N. Boross、Jeffrey W. Bode

  DOI：10.1021/acs.joc.9b02271

  日期：2020.2.7

  The α-ketoacid-hydroxylamine (KAHA) ligation allows the coupling of unprotected peptide segments. Currently, the most applied hydroxylamine is the 5-membered cyclic hydroxylamine (S)-5-oxaproline, which forms a homoserine ester as the primary ligation product. In order to access native aspartic acid residues at the ligation site, we synthesized a 4,4-difluoro version of this monomer. Upon KAHA ligation

  α-酮酸-羟胺（KAHA）连接可以偶联未保护的肽段。当前，最常用的羟胺是5-元环状羟胺（S）-5-氧杂脯氨酸，其形成高丝氨酸酯作为主要的连接产物。为了在连接位点获得天然天冬氨酸残基，我们合成了该单体的4,4-二氟版本。KAHA连接后，生成的二氟醇水解为天冬氨酸残基，几乎没有或没有天冬酰胺形成。我们将该单体用于激素肽胰高血糖素和胰岛素变体的合成，以及肽UbcH5a和SUMO3的片段连接。
• Acetylene-free synthesis of vinyloxy pyridine and quinoline
  作者：Abdelrahman Hamdi、Amany S. Mostafa、Cedric Nana Watat、Mathieu Y. Laurent、Kawther Ben Ayed、Khalid B. Selim、Gilles Dujardin

  DOI：10.1016/j.tetlet.2016.11.061

  日期：2016.12

  Copper-catalyzed vinylation of 2- and 4-hydroxy pyridine and quinoline affords exclusively N-vinylation products. However, vinyl ethers of 4-hydroxy pyridine and quinoline can be prepared via a three-step sequence involving copper-catalyzed C-O cross coupling reaction of the corresponding N-heteroaryl bromides with ethylene glycol, chlorination of the terminal alcohol, and dehydrohalogenation of the

  铜催化的2-和4-羟基吡啶和喹啉的乙烯基化仅提供N-乙烯基化产物。但是，可以通过三步法制备4-羟基吡啶和喹啉的乙烯基醚，该过程涉及相应的N-杂芳基溴化物与乙二醇的铜催化CO交叉偶联反应，末端醇的氯化和β的脱卤化氢。 -氯醚。尽管在2-羟基系列中效率不高，但是该方法可以方便地应用于以中等到良好的总产率制备各种氮杂-芳基乙烯基醚。
• Sequential α-Ketoacid-Hydroxylamine (KAHA) Ligations: Synthesis of C-Terminal Variants of the Modifier Protein UFM1
  作者：Ayodele O. Ogunkoya、Vijaya R. Pattabiraman、Jeffrey W. Bode

  DOI：10.1002/anie.201204144

  日期：2012.9.17

  α‐ketoacid–hydroxylamine (KAHA) ligations with 5‐oxaproline allow access to the modifier protein UFM1 (Ubiquitin‐fold modifier 1) with a C‐terminal amide, carboxylic acid, or a masked thioester. Fmoc protection of an N‐terminal 5‐oxaproline permits the assembly of proteins of >80 residues in good yield by a two‐pot process from three readily prepared medium‐sized protein segments.

  3比3：与5-氧杂脯氨酸的顺序α-酮酸-羟胺（KAHA）连接可访问带有C末端酰胺，羧酸或掩蔽的硫酯的修饰蛋白UFM1（泛素修饰1）。N-末端5-氧杂脯氨酸的Fmoc保护可以通过两锅法从三个容易制备的中等大小蛋白质片段中以高收率组装大于80个残基的蛋白质。
• Chemical Protein Synthesis by Chemoselective α-Ketoacid-Hydroxylamine (KAHA) Ligations with 5-Oxaproline
  作者：Vijaya R. Pattabiraman、Ayodele O. Ogunkoya、Jeffrey W. Bode

  DOI：10.1002/anie.201200907

  日期：2012.5.21

  The chemical synthesis of proteins from unprotected peptide segments uses KAHA ligation with 5‐oxaproline, which is incorporated readily into peptides by solid‐phase peptide synthesis. Ligation of such protein segments in aqueous buffers with an α‐ketoacid peptide gives an α‐homoserine residue at the ligation site. The new ligation is used for the synthesis of two proteins, prokaryotic‐ubiquitin like

  来自未保护肽段的蛋白质化学合成使用KAHA与5-氧杂脯氨酸的连接，通过固相肽合成很容易将其掺入肽中。在水性缓冲液中将此类蛋白质片段与α-酮酸肽连接，可在连接位点产生α-高丝氨酸残基。新的连接用于合成两种蛋白，原核泛素样蛋白（Pup）和可能的冷休克蛋白A（cspA；参见方案）。
• α,α-Dichloroisoxazolidinones for the Synthesis and Chemoselective Peptide Ligation of α-Peptide α-Ketoacids
  作者：Jeffrey W. Bode、Tetsuo Narumi

  DOI：10.3987/com-10-s(e)106

  日期：——

  In seeking to develop an iterative approach to the preparation of alpha-oligopeptides by the chemoselective amide-forming coupling of alpha-ketoacids and hydroxylamines, we have designed and synthesized novel enantiopure monomers. Key to our approach is the use of alpha,alpha-dichloroacids as masked alpha-ketoacids. The preparation of these monomers, their coupling with alpha-ketoacids, and the conversion of the alpha,alpha-dichloroacids to alpha-ketoacids is described. These studies provide a first step to a conceptually unique approach to peptide synthesis that does not require activating reagents or produce chemical byproducts.