Iyengar B S, Remers W A
J Med Chem. 1985 Jul;28(7):963-7. doi: 10.1021/jm00145a021.
Two mechanisms proposed for the acid-catalyzed conversions of mitomycins into mitosenes were investigated by deuterium incorporation methods. Four different mitomycins, an aziridinomitosene, and an N-acetylmitomycin all underwent the conversion in acetic acid-d with no incorporation of deuterium at C-1. This evidence suggests that the mechanism based on initial elimination of the elements of methanol to give an aziridinomitosene is more likely the correct one. The products of these reactions had considerable variation in the ratios of cis to trans isomers: 7-aminomitosanes gave a predominance of trans and 7-methoxymitosanes gave a predominance of cis. Treatment of mitomycin C with DCl in D2O gave predominantly cis product with about 45% deuterium exchange at C-1. The isomeric 2,7-diamino-1-methoxymitosenes previously obtained by treating mitomycin C in methanol containing acetic acid were found to have stereochemistry opposite to that originally assigned by us.
通过氘掺入法研究了两种关于丝裂霉素在酸催化下转化为丝裂烯的机制。四种不同的丝裂霉素、一种氮丙啶丝裂烯和一种N - 乙酰丝裂霉素在氘代乙酸中均发生了转化，且在C - 1位没有氘掺入。这一证据表明，基于最初消除甲醇元素生成氮丙啶丝裂烯的机制更有可能是正确的。这些反应的产物在顺式和反式异构体比例上有相当大的差异：7 - 氨基丝裂烷以反式为主，7 - 甲氧基丝裂烷以顺式为主。在重水中用DCl处理丝裂霉素C，主要得到顺式产物，C - 1位有大约45%的氘交换。之前通过在含乙酸的甲醇中处理丝裂霉素C得到的异构2,7 - 二氨基 - 1 - 甲氧基丝裂烯，其立体化学结构与我们最初指定的相反。
