N(1a)-(toluenesulfonyl)mitomycin C | 5091-32-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吲哚及其衍生物
• 英文名称: N(1a)-(toluenesulfonyl)mitomycin C
• 英文别名: Azirino(2',3':3,4)pyrrolo(1,2-a)indole-4,7-dione, 1,1a,2,8,8a,8b-hexahydro-6-amino-8-(hydroxymethyl)-8a-methoxy-5-methyl-1-(p-tolylsulfonyl)-, carbamate (beta)；[(4S,6S,7R,8S)-11-amino-7-methoxy-12-methyl-5-(4-methylphenyl)sulfonyl-10,13-dioxo-2,5-diazatetracyclo[7.4.0.02,7.04,6]trideca-1(9),11-dien-8-yl]methyl carbamate
• CAS: 5091-32-7
• 化学式: C₂₂H₂₄N₄O₇S
• 分子量: 488.521
• InChiKey: WWBNQTBDBRHPRV-YKLQFZGNSA-N

物化性质

• 沸点：
  723.1±70.0 °C(Predicted)
• 密度：
  1.59±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  34
• 可旋转键数：
  6
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.41
• 拓扑面积：
  171
• 氢给体数：
  2
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  N(1a)-(toluenesulfonyl)mitomycin C 在 platinum(IV) oxide Tris-DCl-buffer pD 5.50 、 氢气 、 重水 作用下， 以41%的产率得到1-deuterio-2-<(toluenesulfonyl)amino>-7-aminomitosene
  参考文献：
  名称：

  Studies on the mechanism of mitomycin C(1) electrophilic transformations: structure-reactivity relationships

  摘要：

  Previous studies have demonstrated that reductive activation of mitomycin C (1) under acidic conditions furnished high yields of the C(1) electrophilic product 2,7-diaminomitosene (5). This adduct was also the major metabolite produced upon administration of 1 to HT-29 cytosol, purified HT-29 colon carcinoma cells, and rat hepatic DT-diaphorase. Proton capture at C(1) in 1 is known to proceed with high stereoselectivity. Information concerning the mechanism and the controlling factors that govern this transformation have been determined by examining the structure-reactivity relationship for mitomycin C (1), 10-decarbamoylmitomycin C (10), N(1a)-methyl-10-decarbamoyl-10-acetoxymitomycin C (11), mitomycin D (12), 10-decarbamoylmitomycin D (13), 7-aminoaziridinomitosene (14), N(1a)-(methanesulfonyl)mitomycin C (15), and N(1a)-(toluenesulfonyl)mitomycin C (16). The combined results obtained were consistent with the hypothesis that mitomycin C C(1) electrophilic reactions funneled through quinone methide 4. The high stereoselectivity of this process has been attributed (in part) to the protonated C(2) amino group in 4. In this scenario, proton capture occurred preferentially from the site opposite to the C(2) ammonium group in order to minimize adverse coulombic interactions.

  DOI：

  10.1021/jo00032a037
• 作为产物：
  描述：

  丝裂霉素 C 、 对甲苯磺酰氯 在 吡啶 、 三乙胺 作用下， 反应 0.33h， 以70%的产率得到N(1a)-(toluenesulfonyl)mitomycin C
  参考文献：
  名称：

  Studies on the mechanism of mitomycin C(1) electrophilic transformations: structure-reactivity relationships

  摘要：

  Previous studies have demonstrated that reductive activation of mitomycin C (1) under acidic conditions furnished high yields of the C(1) electrophilic product 2,7-diaminomitosene (5). This adduct was also the major metabolite produced upon administration of 1 to HT-29 cytosol, purified HT-29 colon carcinoma cells, and rat hepatic DT-diaphorase. Proton capture at C(1) in 1 is known to proceed with high stereoselectivity. Information concerning the mechanism and the controlling factors that govern this transformation have been determined by examining the structure-reactivity relationship for mitomycin C (1), 10-decarbamoylmitomycin C (10), N(1a)-methyl-10-decarbamoyl-10-acetoxymitomycin C (11), mitomycin D (12), 10-decarbamoylmitomycin D (13), 7-aminoaziridinomitosene (14), N(1a)-(methanesulfonyl)mitomycin C (15), and N(1a)-(toluenesulfonyl)mitomycin C (16). The combined results obtained were consistent with the hypothesis that mitomycin C C(1) electrophilic reactions funneled through quinone methide 4. The high stereoselectivity of this process has been attributed (in part) to the protonated C(2) amino group in 4. In this scenario, proton capture occurred preferentially from the site opposite to the C(2) ammonium group in order to minimize adverse coulombic interactions.

  DOI：

  10.1021/jo00032a037

文献信息

• Studies on the mechanism of mitomycin C(1) electrophilic transformations: structure-reactivity relationships
  作者：Insook Han、David J. Russell、Harold Kohn

  DOI：10.1021/jo00032a037

  日期：1992.3

  Previous studies have demonstrated that reductive activation of mitomycin C (1) under acidic conditions furnished high yields of the C(1) electrophilic product 2,7-diaminomitosene (5). This adduct was also the major metabolite produced upon administration of 1 to HT-29 cytosol, purified HT-29 colon carcinoma cells, and rat hepatic DT-diaphorase. Proton capture at C(1) in 1 is known to proceed with high stereoselectivity. Information concerning the mechanism and the controlling factors that govern this transformation have been determined by examining the structure-reactivity relationship for mitomycin C (1), 10-decarbamoylmitomycin C (10), N(1a)-methyl-10-decarbamoyl-10-acetoxymitomycin C (11), mitomycin D (12), 10-decarbamoylmitomycin D (13), 7-aminoaziridinomitosene (14), N(1a)-(methanesulfonyl)mitomycin C (15), and N(1a)-(toluenesulfonyl)mitomycin C (16). The combined results obtained were consistent with the hypothesis that mitomycin C C(1) electrophilic reactions funneled through quinone methide 4. The high stereoselectivity of this process has been attributed (in part) to the protonated C(2) amino group in 4. In this scenario, proton capture occurred preferentially from the site opposite to the C(2) ammonium group in order to minimize adverse coulombic interactions.