methyl 2-azidocarbonyl-(1R,2S)-cyclobutane-1-carboxylate | 221158-92-5

• 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: methyl 2-azidocarbonyl-(1R,2S)-cyclobutane-1-carboxylate
• 英文别名: methyl (1R,2S)-2-carbonazidoylcyclobutane-1-carboxylate
• CAS: 221158-92-5
• 化学式: C₇H₉N₃O₃
• 分子量: 183.167
• InChiKey: NIYGUMJXVIEXLZ-CRCLSJGQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  57.7
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  methyl 2-azidocarbonyl-(1R,2S)-cyclobutane-1-carboxylate 在 氯甲酸乙酯 、 三乙胺 、 sodium hydroxide 作用下， 以 四氢呋喃 、 水 、 丙酮 、 甲苯 为溶剂， 反应 17.5h， 生成 (-)-(1R,2S)-2-(t-butyloxycarbonylamino)cyclobutane-carboxamide
  参考文献：
  名称：

  Stereoselective Synthesis of All Stereoisomers of Orthogonally Protected Cyclobutane-1,2-diamine and Some Chemoselective Transformations

  摘要：

  The four stereoisomers of protected cyclobutane-1,2-diamine have been prepared in an enantio- and diastereocontrolled manner through stereodivergent synthetic routes starting from a half-ester as a common chiral precursor. Orthogonal protection allows the chemoselective manipulation of both amino groups as shown in this work.

  DOI：

  10.1021/ol300689e
• 作为产物：
  描述：

  顺式-环丁烷-1,2-二羧酸 在 sodium azide 、 pig liver esterase 、 水 、 三乙胺 作用下， 生成 methyl 2-azidocarbonyl-(1R,2S)-cyclobutane-1-carboxylate
  参考文献：
  名称：

  Stereoselective synthesis of (−)-(1R,2S)-2-aminocyclobutane-1-carboxylic acid, a conformationally constrained β-amino acid

  摘要：

  The title compound as well as some derivatives have been synthesized for the first time in optically active form by means of a chemoenzymatic transformation used to induce asymmetry in achiral precursors. The enantio- and diastereomeric purity has been determined by HPLC and NMR techniques. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(98)00462-5

文献信息

• (+)- and (−)-2-Aminocyclobutane-1-carboxylic Acids and Their Incorporation into Highly Rigid β-Peptides:  Stereoselective Synthesis and a Structural Study
  作者：Sandra Izquierdo、Federico Rúa、Abdelouahid Sbai、Teodor Parella、Ángel Álvarez-Larena、Vicenç Branchadell、Rosa M. Ortuño

  DOI：10.1021/jo0510843

  日期：2005.9.1

  Several derivatives of (+)- and (−)-2-aminocyclobutane-1-carboxylic acid, 1, have been prepared through enantiodivergent synthetic sequences. The stereoselective synthesis of free amino acid (+)-1 has been achieved, and this product has been fully characterized for the first time. Stereocontrolled alternative synthetic methodologies have been developed for the preparation of bis(cyclobutane) β-dipeptides

  通过对映异构的合成序列已经制备了（+）-和（-）-2-氨基环丁烷-1-羧酸1的几种衍生物。立体选择性合成游离氨基酸（+）- 1已实现，并且此产品已首次全面表征。已经开发了立体控制的替代合成方法以高产率制备双（环丁烷）β-二肽。其中，已经合成了对映体和非对映体。还已经制备了由环丁烷残基和线性氨基酸的偶联产生的β，β-和β，δ-二聚体。已经显示出环丁烷环作为单体和二聚体中的结构促进单元的能力。NMR结构研究和DFT理论计算证明了强分子内分子的形成氢键产生顺式[4.2.0]辛烷结构单元，在溶液和气相中均赋予这些分子高刚性。还观察到了由围绕氨基甲酸酯NC（O）键旋转引起的顺式-反式构象平衡的贡献，反式是主要的构象体。在固态中，不存在该平衡，此外，存在分子间氢键。
• Folding and self-assembling with β-oligomers based on (1R,2S)-2-aminocyclobutane-1-carboxylic acid
  作者：Elisabeth Torres、Esther Gorrea、Kepa K. Burusco、Eric Da Silva、Pau Nolis、Federico Rúa、Stéphanie Boussert、Ismael Díez-Pérez、Samantha Dannenberg、Sandra Izquierdo、Ernest Giralt、Carlos Jaime、Vicenç Branchadell、Rosa M. Ortuño

  DOI：10.1039/b918755c

  日期：——

  Improved methodologies are provided to synthesize (1R,2S)-2-aminocyclobutane-1-carboxylic acid derivatives and their incorporation into β-peptides of 2–8 residues bearing different N-protecting groups. The conformational analysis of these oligomers has been carried out by using experimental techniques along with theoretical calculations. This study shows that these oligomers adopt preferentially a strand-type conformation in solution induced by the formation of intra-residue six-membered hydrogen-bonded rings, affording cis-fused [4.2.0]octane structural units that confer high rigidity on these β-peptides. Moreover, all of them are prone to self-assemble producing nano-sized fibres, as evidenced by TEM, AFM and SPFM, and, in some instances, they also form gels. These techniques and molecular modelling allowed us to suggest an aggregation model for the assembly structures in which a parallel molecular-arrangement is preferred and the conformation is similar to that observed in solution. According to this model, both hydrogen-bonding and hydrophobic interactions would account for formation of the assemblies.

  本研究提供了改进的方法来合成(1R,2S)-2-氨基环丁烷-1-羧酸衍生物，并将其加入带有不同 N 保护基团的 2â8 个残基的 δ 肽中。通过实验技术和理论计算，对这些低聚物进行了构象分析。研究结果表明，这些低聚物在溶液中优先采用的是由残基内六元氢键环的形成所诱导的链型构象，形成顺式融合的[4.2.0]辛烷结构单元，赋予这些δ肽高刚性。此外，正如 TEM、AFM 和 SPFM 所证明的那样，所有这些δ肽都容易自组装生成纳米级纤维，在某些情况下，它们还能形成凝胶。通过这些技术和分子建模，我们提出了一种组装结构的聚集模型，在该模型中，平行分子排列是首选，其构象与溶液中观察到的构象相似。根据该模型，氢键和疏水相互作用都是形成组装体的原因。
• Chiral Cyclobutane-Based Ureas as Versatile Platforms to Tune Structural Diversity: An Experimental and Theoretical Approach
  作者：Ona Illa、Eric Da Silva、Elisabeth Torres、Ángel Álvarez-Larena、Klaus Wurst、Rosa M. Ortuño、Vicenç Branchadell

  DOI：10.1021/acs.cgd.3c01467

  日期：2024.4.3

  Four new chiral 2,2′-disubstituted biscyclobutane ureas have been synthesized and crystallized. Each of them bears a different substituent on positions 2,2′, that is, esters, hydroxymethyl groups, and carboxyl groups. The mode of aggregation of each urea in the crystal packing to form chains, helices, sheets, and others is tuned both by the intermolecular hydrogen bonds between the urea groups and

  合成并结晶了四种新的手性2,2'-二取代双环丁烷脲。它们各自在2,2'位上带有不同的取代基，即酯、羟甲基和羧基。晶体堆积中每个脲形成链、螺旋、片等的聚集模式是通过脲基团之间的分子间氢键和取代基产生额外氢键的不同能力来调节的。借助计算计算使实验结果合理化，从而可以了解能量因素对观察到的优先结构稳定的贡献。
• Enantioselective synthetic approaches to cyclopropane and cyclobutane β-amino acids: synthesis and structural study of a conformationally constrained β-dipeptide
  作者：Marta Martı́n-Vilà、Elena Muray、Gemma P Aguado、Angel Alvarez-Larena、Vicenç Branchadell、Cristina Minguillón、Ernest Giralt、Rosa M Ortuño

  DOI：10.1016/s0957-4166(00)00297-4

  日期：2000.9

  Synthetic approaches to carbocyclic compounds, namely cyclopropane and cyclobutane beta -amino acids, are presented. One of them is based on enzymatic desymmetrization of meso diesters, leading to the enantioselective production of cis-hemiesters, which afforded beta -amino acids through Curtius rearrangements. The enantiomeric excess for the cyclobutane derivatives was 91% whereas the cyclopropanes were obtained in 63% ee. According to another strategy, an enantiomerically pure cyclopropane trans-beta -amino acid, bearing a quaternary center, has been synthesized from a homochiral precursor easily available from D-glyceraldehyde. The preparation and structural investigation of the first synthesized cyclobutane containing dipeptide is also described. A hairpin-like conformation of this molecule in the solid state has been demonstrated by X-ray structural analysis, showing crystal packing induced by the presence of the rigid cyclobutane moiety and the formation of intermolecular hydrogen bonds. NMR experiments confirmed that these molecules also tend to produce aggregates in solution. On the contrary, theoretical calculations suggest that intramolecular interactions are important in the gas phase, as expected. (C) 2000 Elsevier Science Ltd. All rights reserved.