Structure and stereochemistry of some 1,2-disubstituted mitosenes from solvolysis of mitomycin C and Mitomycin A

摘要: Starting with mitomycin C (1), a number of solvolytic reactions were investigated and found to result in opening the aziridine ring loss or migration 9a-methoxy group. A careful examination resulting 1,2-disubstituted 7-aminomitosenes indicated that there was strong tendency for azridine on furnish mainly one stereoisomer, always oxygen stom at C-1 nitrogen atom C-2. Thus hydrolysis 1withdition small amounts trans-aminohydrin (10). Mitomycin (2) BEHAVED ANALOGOUSLY. Both 1 2 generated cis-1-acetoxy-2-acetamide when they allowed react acetic anhydride. Acetolysis give cis-1-hydroxy-2-acetamide (5), trans-1-acetoxy-2-amine (14), cis-trans mixture 1-acetoxy-2-acetamides (4 11, respectively). Routes cis-1-methoxy-2-acetamide (9) possible through methanolysis methylation 5. For comparison, trans-1-methoxy-2-acetamide (16) obtained dnown resin-catalyzed methoxy from C-9A TO IN MITOMYCIN C. The use 1-H nmr spectroscopy asign configurations mitosenes is discussed.