2.3-Epoxy-2-methyl-butanal-(1) | 55771-42-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 环氧化物
• 英文名称: 2.3-Epoxy-2-methyl-butanal-(1)
• 英文别名: 2,3-dimethyl-oxiranecarbaldehyde；2,3-Dimethyl-2,3-epoxypropanal；2,3-dimethyloxirane-2-carbaldehyde
• CAS: 55771-42-1
• 化学式: C₅H₈O₂
• 分子量: 100.117
• InChiKey: QNGSMNKKKBGYJJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0
• 重原子数：
  7
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  29.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2.3-Epoxy-2-methyl-butanal-(1) 在 sodium azide 、 氯化铵 、 三乙胺 、 三苯基膦 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 12.25h， 生成 (2R,3S)-N-Boc-2-<(E)-2-(methoxycarbonyl)ethenyl>-2,3-dimethylaziridine
  参考文献：
  名称：

  SN2'-Reactions of Peptide Aziridines. A Cuprate-Based Approach to (E)-Alkene Isosteres

  摘要：

  Alkenylaziridines were prepared from allylic alcohols via Sharpless epoxidation; oxirane to aziridine conversion under modified Staudinger conditions, and Wittig chain extension. Alternatively, beta-hydroxy alpha-amino acids such as threonine can serve as readily available precursors. The corresponding N-acyl, -peptidyl-, -carbamoyl-, and -sulfonylaziridines underwent a high-yielding anti-S(N)2' alkylation with organocopper/BF3 complex to give (E)-alkene peptide isosteres in 62 to >98% de. The stereoselectivity of the addition process was studied by H-1 and F-19 NMR as well as chemical degradation. Alkene isosteres are important nonhydrolyzable and rigidified analogs of peptide bonds in biologically active peptides. This new methodology considerably facilitates the synthesis and the study of these peptide mimetics, since alkenylaziridines are readily prepared and side-chain modification is simplified by the wide range of functionalized organocopper reagents that are available.

  DOI：

  10.1021/jo00096a033
• 作为产物：
  描述：

  2-Methyl-2,3-epoxy-1-butanol 在 草酰氯 、 二甲基亚砜 、 三乙胺 作用下， 生成 2.3-Epoxy-2-methyl-butanal-(1)
  参考文献：
  名称：

  SN2'-Reactions of Peptide Aziridines. A Cuprate-Based Approach to (E)-Alkene Isosteres

  摘要：

  Alkenylaziridines were prepared from allylic alcohols via Sharpless epoxidation; oxirane to aziridine conversion under modified Staudinger conditions, and Wittig chain extension. Alternatively, beta-hydroxy alpha-amino acids such as threonine can serve as readily available precursors. The corresponding N-acyl, -peptidyl-, -carbamoyl-, and -sulfonylaziridines underwent a high-yielding anti-S(N)2' alkylation with organocopper/BF3 complex to give (E)-alkene peptide isosteres in 62 to >98% de. The stereoselectivity of the addition process was studied by H-1 and F-19 NMR as well as chemical degradation. Alkene isosteres are important nonhydrolyzable and rigidified analogs of peptide bonds in biologically active peptides. This new methodology considerably facilitates the synthesis and the study of these peptide mimetics, since alkenylaziridines are readily prepared and side-chain modification is simplified by the wide range of functionalized organocopper reagents that are available.

  DOI：

  10.1021/jo00096a033

文献信息

• Über die synthese und eigenschaften einiger isomeren chlorhydroxyaldehyde
  作者：Z. Jedlinski、J. Majnusz

  DOI：10.1016/s0040-4020(01)82829-5

  日期：1969.1

  The paper describes the synthesis and properties of some isomeric chlorhydroxyaldehydes, obtained as the result of reactions between epoxyaldehydes and hydrogen chloride, or between unsaturated aldehydes and hypochlorous acid. The mechanisms of these syntheses are also suggested, as well as the course of the dimerisation of isomeric chlorhydroxyaldehydes.

  该论文描述了一些异构的氯羟醛的合成和性质，这些氯羟醛是环氧醛与氯化氢之间或不饱和醛与次氯酸之间反应的结果。还提出了这些合成的机理，以及异构的氯羟醛二聚化的过程。
• Diastereoselective Epoxidation of Oxazolidine-Substituted Alkenes by Dimethyldioxirane and <i>m</i>-Chloroperbenzoic Acid:  π-Facial Control through Hydrogen Bonding by the Urea Functionality
  作者：Waldemar Adam、Simon B. Schambony

  DOI：10.1021/ol006800w

  日期：2001.1.1

  [figure: see text] A high diastereoselectivity (up to > 98:2) is found for the DMD and m-CPBA epoxidations of chiral oxazolidine-substituted olefins with a urea group. The selectivity is explained in terms of hydrogen bonding between the remote NH group of the urea functionality and the epoxidizing reagent. Methylation of the NH group prohibits hydrogen bonding, and a reversed selectivity is observed

  [图：见正文]发现具有脲基的手性恶唑烷取代的烯烃的DMD和m-CPBA环氧化具有很高的非对映选择性（高达> 98：2）。用脲官能团的远端NH基团与环氧化试剂之间的氢键来解释选择性。NH基团的甲基化阻止氢键合，并且由于试剂和尿素官能团之间的空间排斥而观察到相反的选择性。
• SN2'-Reactions of Peptide Aziridines. A Cuprate-Based Approach to (E)-Alkene Isosteres
  作者：Peter Wipf、Paul C. Fritch

  DOI：10.1021/jo00096a033

  日期：1994.8

  Alkenylaziridines were prepared from allylic alcohols via Sharpless epoxidation; oxirane to aziridine conversion under modified Staudinger conditions, and Wittig chain extension. Alternatively, beta-hydroxy alpha-amino acids such as threonine can serve as readily available precursors. The corresponding N-acyl, -peptidyl-, -carbamoyl-, and -sulfonylaziridines underwent a high-yielding anti-S(N)2' alkylation with organocopper/BF3 complex to give (E)-alkene peptide isosteres in 62 to >98% de. The stereoselectivity of the addition process was studied by H-1 and F-19 NMR as well as chemical degradation. Alkene isosteres are important nonhydrolyzable and rigidified analogs of peptide bonds in biologically active peptides. This new methodology considerably facilitates the synthesis and the study of these peptide mimetics, since alkenylaziridines are readily prepared and side-chain modification is simplified by the wide range of functionalized organocopper reagents that are available.