(2S,3S)-(+)-N-(p-toluenesulfinyl)-2-carbomethoxy-3-phenylaziridine

• 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: (2S,3S)-(+)-N-(p-toluenesulfinyl)-2-carbomethoxy-3-phenylaziridine
• 英文别名: (2S,3S)-(+)-N-p-toluenesulfinyl-2-carbomethoxy-3-phenylaziridine；methyl (2S,3S)-1-(4-methylphenyl)sulfinyl-3-phenylaziridine-2-carboxylate
• 化学式: C₁₇H₁₇NO₃S
• 分子量: 315.393
• InChiKey: UMPUHHVBBMHJPU-RVOGRPJXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  22
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.24
• 拓扑面积：
  65.6
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (2S,3S)-(+)-N-(p-toluenesulfinyl)-2-carbomethoxy-3-phenylaziridine 在 钯 甲酸 、 间氯过氧苯甲酸 作用下， 以 乙醇 、 氯仿 为溶剂， 反应 5.0h， 生成 N-(p-toluenesulfonyl)-L-phenylalanine methyl ester
  参考文献：
  名称：

  Asymmetric Synthesis and Reactions of cis-N-(p-Toluenesulfinyl)aziridine-2-carboxylic Acids

  摘要：

  cis-Aziridine-2-carboxylic acids, 2, precursors of the difficult to prepare syn-beta-hydroxy-alpha-amino acid structural unit, are prepared in high diastereomeric purity by a Darzens-type reaction of the lithium enolate of methyl bromoacetate with enantiopure sulfinimines 1.

  DOI：

  10.1021/jo00091a001
• 作为产物：
  描述：

  溴乙酸甲酯 、 (S,E)-N-benzylidene-4-methylbenzenesulfinamide 在 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 为溶剂， 以77%的产率得到(2S,3S)-(+)-N-(p-toluenesulfinyl)-2-carbomethoxy-3-phenylaziridine
  参考文献：
  名称：

  Asymmetric Synthesis and Reactions of cis-N-(p-Toluenesulfinyl)aziridine-2-carboxylic Acids

  摘要：

  cis-Aziridine-2-carboxylic acids, 2, precursors of the difficult to prepare syn-beta-hydroxy-alpha-amino acid structural unit, are prepared in high diastereomeric purity by a Darzens-type reaction of the lithium enolate of methyl bromoacetate with enantiopure sulfinimines 1.

  DOI：

  10.1021/jo00091a001

文献信息

• Asymmetric Synthesis of 2<i>H</i>-Azirine 2-Carboxylate Esters
  作者：Franklin A. Davis、Hu Liu、Chang-Hsing Liang、G. Venkat Reddy、Yulian Zhang、Tianan Fang、Donald D. Titus

  DOI：10.1021/jo991389f

  日期：1999.11.1

  sulfenic acid (RSOH) from nonracemic N-sulfinylaziridine 2-carboxylate esters (4). Optimum yields were obtained when the aziridine was treated with TMSCl at -95 degrees C followed by LDA, which was attributed to the improved leaving group ability of an silicon-oxonium species. By using this new methodology the first asymmetric syntheses of the marine cytotoxic antibiotics (R)-(-)- and (S)-(+)-dysidazirine

  最小的不饱和氮杂环2H-Azirine 2-羧酸酯（5）可通过从非外消旋N-亚磺酰基氮丙啶2​​-羧酸酯（4）中碱诱导的亚磺酸（RSOH）的消除，轻松制备成对映体纯形式。当在-95℃下用TMCSI随后用LDA对氮丙啶进行处理时，可获得最佳产率，这归因于硅-氧鎓物种的离去基团能力提高。通过使用这种新方法，完成了海洋细胞毒性抗生素（R）-（-）-和（S）-（+）-dysidazirine（2）的第一个不对称合成。
• Aziridine compounds, methods of preparation and reactions thereof
  申请人：Drexel University

  公开号：US05789599A1

  公开（公告）日：1998-08-04

  Novel N-sulfinyl-2-carboxyaziridine compounds and novel N-hydrogen-2-hydroxymethylaziridine compounds are provided. The asymmetric synthesis of N-sulfinylaziridines is readily accomplished in high diastereomeric purity and good yield by the Darzens-type reaction of the metal enolate of an .alpha.-haloester and an enantiopure sulfinimine. Ring-opening of these aziridines affords .alpha.-amino acids and the otherwise difficult to prepare syn-.beta.-hydroxy-.alpha.-amino acids, both key structural units found in many bioactive materials. The N-sulfinyl radical may be selectively removed from the novel aziridine compounds by treatment with acid or base. Alternatively, the N-sulfinyl radical may be oxidized to provide the corresponding N-sulfonyl-aziridine, or reduced to form the corresponding 1H-2-hydroxymethylaziridine, either of which may subsequently be ring-opened to provide precursors to bioactive compounds.

  本发明提供了新型N-亚磺酰基-2-羧基环氧丙烷化合物和新型N-氢基-2-羟甲基环氧丙烷化合物。通过α-卤代酯金属烯醇和手性亚磺酰胺的Darzens型反应，可以高度对映异构纯度和良好收率地实现N-亚磺酰基环氧丙烷的不对称合成。这些环氧丙烷的开环反应可得到α-氨基酸和通常难以制备的合成β-羟基-α-氨基酸，这两种结构单元是许多生物活性物质的重要组成部分。新型环氧丙烷化合物中的N-亚磺酰自由基可以通过酸或碱处理进行选择性去除。或者，N-亚磺酰自由基可以氧化为相应的N-磺酰基-环氧丙烷，或还原为相应的1H-2-羟甲基环氧丙烷，随后可以开环形成生物活性化合物的前体。
• Asymmetric Synthesis of β-Substituted α-Amino Acids Using 2<i>H</i>-Azirine-2-carboxylate Esters. Synthesis of 3,3-Disubstituted Aziridine-2-carboxylate Esters
  作者：Franklin A. Davis、Chang-Hsing Liang、Hu Liu

  DOI：10.1021/jo9702610

  日期：1997.6.13
• Asymmetric Synthesis using Sulfinimines (Thiooxime S-Oxides)
  作者：Franklin A. Davis、Padma S. Portonovo、Rajarathnam E. Reddy、G. Venkat Reddy、Ping Zhou

  DOI：10.1080/10426509708545525

  日期：1997.1.1
• Asymmetric Synthesis of 2H-Azirines: First Enantioselective Synthesis of the Cytotoxic Antibiotic (R)-(-)-Dysidazirine
  作者：Franklin A. Davis、G. Venkat Reddy、Hu Liu

  DOI：10.1021/ja00117a050

  日期：1995.3