cis-(2S,3S)-(+)-N-(p-toluenesulfonyl)-2-carbomethoxy-3-phenylaziridine | 158109-81-0

• 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: cis-(2S,3S)-(+)-N-(p-toluenesulfonyl)-2-carbomethoxy-3-phenylaziridine
• 英文别名: (2S,3S)-(+)-N-(p-toluenesulfonyl)-2-carbomethoxy-3-phenylaziridine；methyl (2S,3S)-1-(4-methylphenyl)sulfonyl-3-phenylaziridine-2-carboxylate
• CAS: 158109-81-0
• 化学式: C₁₇H₁₇NO₄S
• 分子量: 331.392
• InChiKey: BLMMFXVDNMRBEW-MZQXSQAVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  23
• 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：
  71.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  cis-(2S,3S)-(+)-N-(p-toluenesulfonyl)-2-carbomethoxy-3-phenylaziridine 在 钯 甲酸 作用下， 以 乙醇 为溶剂， 反应 3.0h， 以89%的产率得到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：

  2-hydroxy-3-(4-methyl benzenesulfonylamino)-3-phenyl-propionic acid methyl ester 生成 cis-(2S,3S)-(+)-N-(p-toluenesulfonyl)-2-carbomethoxy-3-phenylaziridine
  参考文献：
  名称：

  Transition Metal-Catalyzed Regioselective and Stereoselective Aminochlorination of Cinnamic Esters

  摘要：

  [GRAPHICS]A new aminohalogenation process has been developed for the synthesis of vicinal haloamine derivatives using cinnamic esters as substrates. The reaction was performed in CH3CN using ZnCl2 or Cu(OTf)(2) as catalyst and N,N-dichloro-p-toluenesulfonamide as chlorine/nitrogen source. Good to excellent yields and regio- and stereoselectivities have been obtained. The stereochemistry was unambiguously determined by transforming one of the products to a known sample.

  DOI：

  10.1021/ol990059e

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。
• Aza-Darzens Asymmetric Synthesis of <i>N</i>-(<i>p</i>-Toluenesulfinyl)aziridine 2-Carboxylate Esters from Sulfinimines (<i>N</i>-Sulfinyl Imines)
  作者：Franklin A. Davis、Hu Liu、Ping Zhou、Tianan Fang、G. Venkat Reddy、Yulian Zhang

  DOI：10.1021/jo990907j

  日期：1999.10.1

  The one-step aza-Darzens reaction of sulfinimines 2 with lithium alpha-bromoenolates readily affords diversely substituted cis and trans N-sulfinylaziridine 2-carboxylate esters 3 and 7 in good yield and excellent diastereoselectivity. Higher yields, but lower de's, result when a mixture of the alpha-bromo ester and 2 are treated with base. The N-sulfinyl group is transformed, nearly quantitatively, without ring opening, into the N-tosyl activating group by oxidation with m-CPBA. Selective removal of the N-sulfinyl group in aziridines 3a and 3h with TFA/H2O affords VI-aziridines 21 which are difficult to prepared by other means. However, C(3) activated azirines such as 3b undergo ring-opening under these conditions. Alternatively, the N-sulfinyl group, even in C(3)-activated aziridines, was selectively and efficiently removed by treatment of the aziridine with 2 equiv of MeMgBr.
• US5789599A
  申请人：——

  公开号：US5789599A

  公开（公告）日：1998-08-04
• [EN] AZIRIDINE COMPOUNDS, METHODS OF PREPARATION AND REACTIONS THEREOF<br/>[FR] COMPOSES D'AZIRIDINE, PROCEDES DE PREPARATION ET REACTIONS
  申请人：DREXEL UNIVERSITY

  公开号：WO1995030672A1

  公开（公告）日：1995-11-16

  (EN) 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 $g(a)-haloester and an enantiopure sulfinimine. Ring-opening of these aziridines affords $g(a)-amino acids and the otherwise difficult to prepare $i(syn)-$g(b)-hydroxy-$g(a)-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.(FR) Nouveaux composés de N-sulfinyle-2-carboxyaziridine et nouveaux composés de N-hydrogène-2-hydroxyméthylaziridine. La synthèse asymétrique des N-sulfinyl-aziridines s'effectue rapidement avec une pureté diastéréoisomérique élevée et un rendement excellent au moyen de la réaction de Darzens de l'énolat de métal d'un $g(a)-haloester et d'une sulfinimine énantiomériquement pure. L'ouverture du noyau de ces aziridines permet d'obtenir des $g(a)-acides aminés et les acides syn-$g(b)-hydroxy-$g(a)-aminés, qui sont autrement difficiles à préparer, les deux représentant des ensembles structurels clés qu'on trouve dans de nombreux matériaux bioactifs. On peut supprimer sélectivement le radical N-sulfinyle des nouveaux composés d'aziridine par traitement au moyen d'un acide ou d'une base. Dans un autre mode de réalisation, on peut oxyder le radical N-sulfinyle, de manière à obtenir le composé de N-sulfonyle-aziridine correspondant, ou le réduire, afin d'obtenir le composé de 1H-2-hydroxyméthylaziridine correspondant, dont on peut ouvrir ensuite les noyaux, afin d'obtenir des précurseurs de composés bioactifs.