THE DERIVATION OF A NOVEL MITOMYCIN SKELETON: 3α-ALKOXYMITOMYCIN

Abstract

The first example of C-3 alkoxylation in mitomycins has been achieved. 3α-iso-Propoxy-10-O-decarbamoylmitomycin D (4) and 3α-iso-propoxymitomycin D (5) were derived from mitomycin D (3) under decarbamoylation conditions with iso-propoxide. Under similar conditions 3α-iso-propoxy-10-O-decarbamoylporfiromycin (8) and 3α-methoxy-10-O-decarbamoylmitomycin B (11) were also derived from porfiromycin (6) and mitomycin B (9), respectively. The mechanism of generation of these novel analogs was based on the premise that the key intermediate of hydroquinone iminium salt (14) was led through the iminium salt (13), followed by alkoxide addition and oxidation.