Hornemann U, Keller P J, Takeda K
J Med Chem. 1985 Jan;28(1):31-6. doi: 10.1021/jm00379a008.
The acid-catalyzed opening of the aziridine ring of mitomycins A and C is known to occur predominantly with cis stereochemistry. We have observed that the presence or absence of a carbamoyl group at C-10 of mitomycin C and in certain of its analogues does not have a significant influence on the stereochemistry of the opening of this ring. The trans product obtained from mitomycin C was shown to be stable when treated with acid under the conditions of its formation. Mitomycin B was also shown to yield predominantly the cis product when it was subjected to acid-catalyzed opening of its aziridine ring. The 1H NMR spectra of acetate derivatives prepared from mitomycin B show two sets of signals that are due to two populations of rotamers. The analysis of these spectra has substantiated several previous spectral assignments. This paper also presents some thoughts on acid-catalyzed bifunctional DNA alkylation by mitomycins and 10-decarbamoyloxy-9-dehydromitomycins.
已知丝裂霉素A和C的氮丙啶环在酸催化下开环主要生成顺式立体化学产物。我们观察到，丝裂霉素C及其某些类似物在C-10位上是否存在氨甲酰基对该环开环的立体化学没有显著影响。由丝裂霉素C得到的反式产物在其形成条件下用酸处理时显示是稳定的。当丝裂霉素B的氮丙啶环进行酸催化开环时，也主要生成顺式产物。由丝裂霉素B制备的乙酸酯衍生物的1H NMR谱显示出两组信号，这归因于两种旋转异构体。对这些谱的分析证实了先前的一些光谱归属。本文还提出了关于丝裂霉素和10-脱氨甲酰氧基-9-脱氢丝裂霉素对DNA进行酸催化双功能烷基化的一些观点。
