benzyl (S)-(4-diazo-3-oxobutan-2-yl)carbamate | 67865-68-3

• 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: benzyl (S)-(4-diazo-3-oxobutan-2-yl)carbamate
• 英文别名: Z-L-Ala-CHN2；benzyl N-[(2S)-4-diazo-3-oxobutan-2-yl]carbamate
• CAS: 67865-68-3
• 化学式: C₁₂H₁₃N₃O₃
• 分子量: 247.254
• InChiKey: DOUDVLKNDXOMIW-VIFPVBQESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  18
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  57.4
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  benzyl (S)-(4-diazo-3-oxobutan-2-yl)carbamate 在 baker's yeast 、 rhodium(II) catalyst 作用下， 生成 ((1S,2S)-2-Hydroxy-1-methyl-3-phenylsulfanyl-propyl)-carbamic acid benzyl ester
  参考文献：
  名称：

  通过α-重氮羰基中间体在有机合成中的手性基团转移

  摘要：

  衍生自N-保护的氨基酸和（S）-2-氯丙酸的旋光重氮酮已经用作合成各种旋光α-官能化酮和相关化合物的手性基团转移试剂。

  DOI：

  10.1039/c39900000362
• 作为产物：
  描述：

  氯甲酸苄酯 在 N-甲基吗啉 、 sodium hydroxide 作用下， 以 四氢呋喃 、 乙醚 、 水 为溶剂， 反应 0.25h， 生成 benzyl (S)-(4-diazo-3-oxobutan-2-yl)carbamate
  参考文献：
  名称：

  Synthesis of enantiopure free and N-benzyloxycarbonyl-protected 3-substituted homotaurines from naturally occurring amino acids

  摘要：

  Enantiopure N-benzyloxycarbonyl-protected and free 3-substituted homotaurines were synthesized from naturally occurring amino acids via N-benzyloxycarbonyl protection, Arndt-Eistert homologation, reduction, esterification with thioacetic acid, and oxidation with performic acid. The current method is a convenient, practical, and salt-free method for the synthesis of enantiopure 3-substituted homotaurine with moderate to good yields. (C) 2014 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2014.05.098

文献信息

• Synthesis of diazoketones derived from α-amino acids; problem of side reactions
  作者：Krystyna Plucińska、Bogdan Liberek

  DOI：10.1016/s0040-4020(01)81643-4

  日期：1987.1

  Optimum conditions of synthesis of eight diazoketones derived from optically active N-(t-butyloxycarbonyl)- and N-benzyloxycarbonylamino acids have been described. The problem of formation of by-products during Arndt-Eistert synthesis of β-homoamino acids at the stage of reaction of mixed anhydride with a weak nucleophile-diazomethane - has been discussed.

  已经描述了合成八种衍生自光学活性的N-（叔丁氧羰基）-和N-苄氧羰基氨基酸的重氮酮的最佳条件。讨论了在混合酸酐与弱亲核试剂-重氮甲烷反应的阶段，在Arndt-Eistert合成β-均氨基酸过程中形成副产物的问题。
• Diazoketones as precursors in β-lactam synthesis. New insights into the mechanism of the photochemically induced Staudinger reaction
  作者：Michael R. Linder、Wolfgang U. Frey、Joachim Podlech

  DOI：10.1039/b105748k

  日期：2001.10.11

  Diazoketones 1–3, derived from suitably protected amino acids (Ala, Val and Tle), have been photochemically rearranged in the presence of imines leading exclusively to trans-arranged 4-aryl- and cinnamoyl-substituted β-lactams 17–33 with up to 84% yield. Selectivities were dependent on the steric demand of the amino acid side-chain ranging from 65 ∶ 35 to 90 ∶ 10. The relative configurations were proved by several X-ray crystal structures and comparison of NMR spectra. Further reactions of the azetidinones at position C-4 have been performed: electron-rich aryl substituents (e.g., 4-methoxyphenyl, furyl and thienyl) could be degraded to carboxylic acids 34 and 35 which were further transformed to acetoxy derivatives (compounds 36 and 37) in a Kolbe reaction of type II. The cinnamoyl group could be oxidized to the formyl group by ozonolysis (→ 38, 39). The mechanism of the photochemically induced β-lactam formation is discussed in detail.

  从适当保护的氨基酸（Ala、Val和Tle）衍生出的Diazoketones 1–3，在亚胺的存在下通过光化学重排，专一生成了产率高达84%的trans-排列的4-芳基和肉桂酰取代的β-内酰胺17–33。选择性取决于氨基酸侧链的立体需求，范围从65:35到90:10。相对构型通过多个X射线晶体结构和NMR光谱的比较得到了证实。对氮丙啶酮C-4位的进一步反应已经进行：电子富集的芳基取代基（如4-甲氧基苯基、呋喃基和噻吩基）可以降解为羧酸34和35，这些羧酸进一步通过Kolbe II型反应转化为乙酰氧基衍生物（化合物36和37）。肉桂酰基可以通过臭氧分解氧化为醛基（→38, 39）。光化学诱导的β-内酰胺形成机制被详细讨论。
• Convenient in situ synthesis of nonracemic N-protected β-amino aldehydes from β-amino acids. Applications in Wittig reactions and heterocycle synthesis
  作者：Simon B. Davies、M.Anthony McKervey

  DOI：10.1016/s0040-4039(98)02573-8

  日期：1999.2

  N-Z-γ-amino alcohols derived from nonracemic β-amino acids are smoothly oxidised by manganese dioxide in acetonitrile to afford aldehydes which can be trapped in situ in Wittig reactions with carbonyl-substituted phosphoranes. The application of this methodology to the synthesis of the alkaloids (S)-(+)-N-BOC-coniie, (S)-(−)-coniceine and a pipecoline precursor is described.

  源自非外消旋β-氨基酸的N - Z -γ-氨基醇在乙腈中被二氧化锰平滑氧化，得到醛，这些醛可在Wittig反应中与羰基取代的磷烷原位捕获。描述了该方法在生物碱（S）-（+）- N -BOC-coniie，（S）-（-）-coniceine和胡椒碱前体的合成中的应用。
• Effective Methods for the Synthesis ofN-Methylβ-Amino Acids from All Twenty Commonα-Amino Acids Using 1,3-Oxazolidin-5-ones and 1,3-Oxazinan-6-ones
  作者：Andrew B. Hughes、Brad E. Sleebs

  DOI：10.1002/hlca.200690235

  日期：2006.11

  N-Methyl β-amino acids are generally required for application in the synthesis of potentially bioactive modified peptides and other oligomers. Previous work highlighted the reductive cleavage of 1,3-oxazolidin-5-ones to synthesise N-methyl α-amino acids. Starting from α-amino acids, two approaches were used to prepare the corresponding N-methyl β-amino acids. First, α-amino acids were converted to

  应用N-甲基β-氨基酸通常是潜在合成具有生物活性的修饰的肽和其他寡聚体的应用。先前的工作强调了1，3-恶唑烷-5-酮的还原裂解以合成N-甲基α-氨基酸。从α-氨基酸开始，使用两种方法来制备相应的N-甲基β-氨基酸。首先，α -氨基酸转化为Ñ甲基α -氨基酸由所谓的“-1,3-恶唑-5-酮的策略”，将它们再由同系阿恩特-艾斯特方法，得到Ñ-protected Ñ -甲基β -氨基酸选自20种常见衍生α -氨基酸。这些化合物的制备产率为23–57％（相对于N-甲基α-氨基酸）。在第二种方法中，可以通过Arndt–Eistert方法将12个N保护的α-氨基酸直接同源，然后将所得的β-氨基酸以30–45％的产率转化为1,3-恶二嗪-6-酮。 。最后，还原裂解以41–63％的收率提供了所需的N-甲基β-氨基酸。
• Synthesis of Optically Active β-Amino Acid <i>N</i>-Carboxyanhydrides
  作者：Jianjun Cheng、Joseph W. Ziller、Timothy J. Deming

  DOI：10.1021/ol000122w

  日期：2000.6.1

  general synthesis of optically active beta-amino acid N-carboxyanhydrides (beta-NCAs) through cyclization of N(beta)-Boc or N(beta)-Cbz beta-amino acids using phosphorus tribromide. The formation of beta-NCAs was confirmed by spectroscopy as well as an X-ray structural determination of beta-homoalanine-N-carboxyanhydride. The beta-NCA molecules could be polymerized in good yield to give optically active

  已经开发了通过使用三溴化磷将Nβ-Boc或Nβ-Cbzβ-氨基酸环化来一般合成旋光性β-氨基酸N-羧基酸酐（β-NCA）的方法。β-NCA的形成已通过光谱法以及β-高丙氨酸-N-羧基酸酐的X射线结构测定得到了证实。β-NCA分子可以以高收率聚合，以产生在溶液中采用稳定手性构象的旋光性聚（β-肽）。例如，通过L-β-高苯丙氨酸-N-羧基酸酐的聚合来合成螺旋低聚物（L-β-高苯丙氨酸）。