N^α,N^ε-bis(benzyloxycarbonyl)-D-lysinal | 138207-66-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: N^α,N^ε-bis(benzyloxycarbonyl)-D-lysinal
• 英文别名: Z-Lys-(Z)-H；benzyl N-[(2S)-1-oxo-6-(phenylmethoxycarbonylamino)hexan-2-yl]carbamate
• CAS: 138207-66-6
• 化学式: C₂₂H₂₆N₂O₅
• 分子量: 398.459
• InChiKey: AAVPTODIUYKSAC-FQEVSTJZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  29
• 可旋转键数：
  13
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  93.7
• 氢给体数：
  2
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  N^α,N^ε-bis(benzyloxycarbonyl)-D-lysinal 在 palladium on activated charcoal 盐酸 、 4 A molecular sieve 、 氢气 、 sodium cyanoborohydride 、 zinc(II) chloride 作用下， 以 甲醇 为溶剂， 25.0 ℃ 、206.84 kPa 条件下， 反应 5.17h， 生成 H-Lysψ(CH2NH)Trp-OMe
  参考文献：
  名称：

  Studies on N-deprotection of ψ(CH₂NH) pseudodipeptide methyl esters. Cyclization to 2-ketopiperazines

  摘要：

  N-Deprotection of Z- and Boc-aminomethylene pseudodipeptide methyl esters yielded not only the expected linear deprotected compounds but also the 2-ketopiperazine cyclic analogues. The extent of lactamization was found to be dependent on the nature of the amino acid, the sequence order, and the deprotection conditions. Hydrogenation of Z-pseudodipeptides containing N-terminal basic amino acids in acidic media afforded linear compounds, while replacement of these basic residues by Leu gave mixtures of linear and cyclic pseudodipeptides. The reverse-sequence analogues, with Lys or Arg at the C-terminus, yielded the corresponding 2-ketopiperazines as the only reaction products. Opposite results were obtained for C-terminal Leu derivatives in which almost no cyclization occurred. Hydrogenation under neutral conditions gave mainly cyclic derivatives, while linear analogues were predominant after treatment of Boc-protected pseudodipeptides with trifluoroacetic acid or HCl.

  DOI：

  10.1039/p19910003117
• 作为产物：
  描述：

  N,N’-双苄氧羰基-L-赖氨酸 在 二异丁基氢化铝 作用下， 以 乙醚 、 正己烷 、 甲苯 为溶剂， 生成 N^α,N^ε-bis(benzyloxycarbonyl)-D-lysinal
  参考文献：
  名称：

  A new method to synthesize .ALPHA.-aminoaldehydes.

  摘要：

  苄氧羰基（Cbz）氨基酸酯通过二异丁基铝氢化物还原为相应的α-氨基醛。通过钠硼氢化物还原得到的Cbz-氨基醇的特定旋转与光学纯材料的比较表明，在硅胶上进行色谱分离会显著导致Cbz-α-氨基醛的变旋现象，这是通过酮-烯醇的互变异构造成的。Cbz-S-Bzl-半胱氨酸易于显著变旋。另一方面，Cbz-NG-硝基精氨酸醛的变旋现象很少。这一事实可能与精氨酸衍生物特有的环状卡宾醇胺结构有关。由粗制Cbz-α-氨基醛制备的半卡宾酮可以不发生变旋地再生成为初始的醛。这些半卡宾酮可能作为肽醛合成的良好起始材料。

  DOI：

  10.1248/cpb.23.3081

文献信息

• Procedure for the Oxidation of β-Amino Alcohols to α-Amino Aldehydes
  作者：Maxim E. Sergeev、Victor B. Pronin、Tatiana L. Voyushina

  DOI：10.1055/s-2005-918918

  日期：——

  A novel procedure for the mild oxidation of β-amino alcohols to α-amino aldehydes using commercially available manganese(IV) oxide is reported. There are several important advantages of the new method, such as high enantiopurity of the reaction and the absence of either over-oxidation or any reaction by-products during the process. A number of N-protected l-α-amino aldehydes was obtained. All new compounds were characterized by their NMR spectra and optical rotation data.

  报道了一种使用市售二氧化锰（IV）的温和氧化反应新方法，将β-氨基醇转化为α-氨基醛。该新方法具有多项重要优势，如反应高度保持对映纯度，且在过程中不会发生过度氧化或产生任何反应副产物。成功制备了多种N-保护的L-α-氨基醛。所有新化合物均通过其核磁共振（NMR）谱图和旋光度数据进行了表征。
• Peptide Fragment Coupling Using a Continuous-Flow Photochemical Rearrangement of Nitrones
  作者：Yuan Zhang、Melissa L. Blackman、Andrew B. Leduc、Timothy F. Jamison

  DOI：10.1002/anie.201300504

  日期：2013.4.8

  amide bond formation by way of a continuous‐flow photochemical rearrangement of nitrones was described (see scheme). Simple aryl‐alkyl amide bonds as well as complex peptide bonds were constructed efficiently with a residence time less than 20 minutes. A tetrapeptide was synthesized in this way and the method could be applied to peptide fragment coupling.

  顺其自然通过被描述硝酮的连续流动光化学重排的方式（参见方案）用于酰胺键形成的一般方法：。简单的芳基-烷基酰胺键以及复杂的肽键可在不到20分钟的停留时间内高效构建。用这种方法合成了四肽，该方法可用于肽片段的偶联。
• Pinacol Cross Coupling of 2-[N-(Alkoxycarbonyl)amino] Aldehydes and Aliphatic Aldehydes by [V2Cl3(THF)6]2[Zn2Cl6]. Synthesis of syn,syn-3-[N-(Alkoxycarbonyl)amino] 1,2-Diols
  作者：Andrei W. Konradi、Scott J. Kemp、Steven F. Pedersen

  DOI：10.1021/ja00083a017

  日期：1994.2

  Slow addition of 2-[N-(alkoxycarbonyl)amino] aldehydes to mixtures of [V 2 Cl 3 (THF) 6 ] 2 [Zn 2 Cl 6 ] and aliphatic aldehydes gave syn,syn-3-[N-(alkoxycarbonyl)amino] 1,2-diols in good yield and high enantiomeric purity (>99:1). The alkyl group of the N-alkoxycarbonyl was shown to influence the yield: Me >allyl>Bn>t-Bu. Only the syn,syn diastereomer was observed (>20:1), except with N-Cbz-alaninal

  将 2-[N-(烷氧基羰基) 氨基] 醛缓慢加入 [V 2 Cl 3 (THF) 6 ] 2 [Zn 2 Cl 6 ] 和脂肪族醛的混合物中，得到 syn,syn-3-[N-(烷氧基羰基)氨基] 1,2-二醇，收率高，对映体纯度高 (>99:1)。N-烷氧基羰基的烷基显示出影响产率：Me>烯丙基>Bn>t-Bu。除了 N-Cbz-丙氨醛 (10:1:1)、O-苄基-N-Cbz-丝氨酸 (7:1) 和 N-Cbz-脯氨酸 (5:1 到 12:1)。一种新的丝氨酸衍生物，N-Cbz-O-TBS-丝氨酸，与正十五醛交叉偶联得到木-DC 18-植物鞘氨醇的衍生物
• A new method to synthesize .ALPHA.-aminoaldehydes.
  作者：AKIRA ITO、RIEKO TAKAHASHI、YOSHIHIKO BABA

  DOI：10.1248/cpb.23.3081

  日期：——

  Benzyloxycarbonyl (Cbz)-amino acid esters were reduced to the corresponding α-aminoaldehydes with diisobutylaluminum hydride. Comparison of specific rotation of the Cbz-aminoalcohols, which were derived from the aldehydes by sodium borohydride reduction, with that of the optically pure material showed that chromatography on a silica gel caused marked racemization in the Cbz-α-aminoaldehyde through keto-enol tautomerism. Cbz-S-Bzl-cysteinal was liable to racemize to a great extent. On the other hand, little racemization occurred in Cbz-NG-nitroargininal. This fact might be accounted for the characteristic cyclic carbinolamine structure of the argininal derivative. The semicarbazones prepared from the crude Cbz-α-aminoaldehydes could be reproduced to the initial aldehydes without racemization. These semicarbazones might be used as good starting materials in peptide aldehyde synthesis.

  苄氧羰基（Cbz）氨基酸酯通过二异丁基铝氢化物还原为相应的α-氨基醛。通过钠硼氢化物还原得到的Cbz-氨基醇的特定旋转与光学纯材料的比较表明，在硅胶上进行色谱分离会显著导致Cbz-α-氨基醛的变旋现象，这是通过酮-烯醇的互变异构造成的。Cbz-S-Bzl-半胱氨酸易于显著变旋。另一方面，Cbz-NG-硝基精氨酸醛的变旋现象很少。这一事实可能与精氨酸衍生物特有的环状卡宾醇胺结构有关。由粗制Cbz-α-氨基醛制备的半卡宾酮可以不发生变旋地再生成为初始的醛。这些半卡宾酮可能作为肽醛合成的良好起始材料。
• A Facile One-pot Synthesis of N α-Urethane Protected 3-Amino Alkyl Isoxazole-5-Carboxylic Acids and their Utility for the Preparation of Isoxazole-Linked Peptidomimetics
  作者：G. Chennakrishnareddy、B. Vasantha、N. Narendra、Vommina V. Sureshbabu

  DOI：10.1007/s10989-011-9256-x

  日期：2011.9

  Cu(I) catalyzed [3+2] cycloaddition of in situ generated N α-Fmoc/Boc/Z-protected amino alkyl nitrile oxide with propiolic acid has led to a new class of 3,5-disubstituted isoxazole-bearing amino acid derivatives. The click chemistry protocol described herein is efficient in furnishing the isoxazole embedded amino acids. These unnatural synthons were subjected to chain extension on N- as well as C-termini

  的Cu（I）催化的[3 + 2]的在原位产生环加成Ñ α -Fmoc /的Boc / Z保护的氨基酸与丙炔酸已经导致了一类新的3,5-二取代的异恶唑轴承氨基酸衍生物烷基氧化腈。本文所述的点击化学方案可有效提供异恶唑嵌入的氨基酸。这些非天然的合成子在N-和C-末端上进行链延伸，以获得带有3，5-二取代的异恶唑的二和三肽类似物。