benzyl (2S)-2-isocyano-3-methylbutanoate | 799779-66-1

• 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 (2S)-2-isocyano-3-methylbutanoate
• CAS: 799779-66-1
• 化学式: C₁₃H₁₅NO₂
• 分子量: 217.268
• InChiKey: PITAJNJMVZQXGW-LBPRGKRZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  30.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  benzyl (2S)-2-isocyano-3-methylbutanoate 在 盐酸 、 异氰酸叔丁酯 、 palladium 10% on activated carbon 、 氢气 作用下， 以 1,4-二氧六环 、 甲醇 、 氯仿 为溶剂， 反应 0.92h， 生成 Boc-D-Ala-MeLeu-MeLeu-MeVal-OH
  参考文献：
  名称：

  Expanding the Limits of Isonitrile-Mediated Amidations: On the Remarkable Stereosubtleties of Macrolactam Formation from Synthetic Seco-Cyclosporins

  摘要：

  The scope of isonitrile-mediated amide bond-forming reactions is further explored in this second-generation synthetic approach to cyclosporine (cyclosporin A). Both type I and type II amidations are utilized in this effort, allowing access to epimeric cyclosporins A and H from a single precursor by variation of the coupling reagents. This work lends deeper insight into the relative acylating ability of the formimidate carboxylate mixed anhydride (FCMA) intermediate, while shedding light on the far-reaching impact of remote stereochemical changes on the effective preorganization of seco-cyclosporins.

  DOI：

  10.1021/ja2103372
• 作为产物：
  描述：

  苯甲醇 在 伯吉斯试剂 、 对甲苯磺酰氯 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 1.5h， 生成 benzyl (2S)-2-isocyano-3-methylbutanoate
  参考文献：
  名称：

  异氰酸酯衍生自氨基酸酯：硒化脲肽模拟物，不对称硒脲和硒代乙内酰脲的简便合成方法和应用。

  摘要：

  α-异氰酸酯与元素硒粉反应制得了一类重要的有机硒化合物-α-异硒氰酸酯4。该反应简单，快速，色谱纯化后，所有异异氰酸酯均已分离为稳定的异氰酸酯。这些迄今未报道的分子类别将是用于制备各种含硒的拟肽的有用的构建单元。在这项研究中，证明了标题分子在制备硒脲脲肽模拟物6，不对称硒脲8和硒乙内酰脲10中的效用。版权所有©2010欧洲肽协会和John Wiley＆Sons，Ltd.。

  DOI：

  10.1002/psc.1276

文献信息

• Preparation and reactions of N-thioformyl peptides from amino thioacids and isonitriles
  作者：Yu Yuan、Jianglong Zhu、Xuechen Li、Xiangyang Wu、Samuel J. Danishefsky

  DOI：10.1016/j.tetlet.2009.02.205

  日期：2009.5

  The preparation of N-thioformyl peptides from amino thioacids and isonitriles at room temperature is described.

  描述了在室温下由氨基硫代酸和异腈制备N-硫甲酰肽。
• 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。
• On the preparation of enantiomerically pure isonitriles from amino acid esters and peptides
  作者：Jianglong Zhu、Xiangyang Wu、Samuel J. Danishefsky

  DOI：10.1016/j.tetlet.2008.11.069

  日期：2009.2

  An improved method for the synthesis of enantiomerically pure isonitriles from amino acid esters and dipeptides is described.

  描述了一种从氨基酸酯和二肽合成对映异构纯异腈的改进方法。
• Three-Component Condensation Leading to β-Amino Acid Diamides:  Convergent Assembly of β-Peptide Analogues
  作者：Jennifer M. Oaksmith、Ulf Peters、Bruce Ganem

  DOI：10.1021/ja0450152

  日期：2004.10.1

  A Passerini condensation of acyl cyanides, carboxylic acids, and isonitriles has been developed that affords efficient access to functionalized diamides as well as beta-peptides of alpha-hydroxy-beta-amino acids. Such compounds are protease-resistant and form stable helical and sheet structures when incorporated into larger peptides. N-Protected alpha-amino acids and isocyanoesters derived from alpha-amino acids participate in the condensation, leading to alpha/beta peptides embodying the heterogeneous alpha/beta/alpha backbone motif, recent examples of which display antibiotic activity.
• On the Synthesis of Conformationally Modified Peptides through Isonitrile Chemistry: Implications for Dealing with Polypeptide Aggregation
  作者：Xiangyang Wu、Peter K. Park、Samuel J. Danishefsky

  DOI：10.1021/ja2023898

  日期：2011.5.25

  A method for introducing a dimethyleneoxy constraint joining the N atoms of two consecutive amino acids in the context of a polypeptide has been developed. This constraint can profoundly affect the tendency of a polypeptide to suffer aggregation and desolubilization, and it can be readily removed under mild conditions.