MICROBIOLOGICAL OXYGENATION OF AZACYCLOALKANES . STRUCTURAL DETERMINATIONS AND SOME CHEMICAL MODIFICATIONS LEADING TO TRANSANNULAR REACTIONS

Microbiological oxygenation with Sporotrichum sulfurescens has been shown to occur at C-4 of 1-benzoylpiperidine (1), at C-3 and C-4 of 1-benzoylhexamethylenimine (6), at C-4 of 1-p-toluenesulfonylhexamethylenimine (7), and at C-4 and C-5 of 1-benzoylheptamethylenimine (15) and 1-benzoyloctamethylemmine (34). Further chemical modifications in the hepta- and octamethylenimine series have led to a number of transannular reactions. Included in these reactions is the conversion of 1-benzoylhexahydro-5(2H)-azocinone (18) into the iminium salt (26) via 9-benzoyl-1,4-dioxa-9-azaspiro[4.7]dodecane (20), 9-benzyl-1,4-dioxa-9-azaspiro[4.7]dodecane (21), and 1,4-dioxa-9-azaspiro[4.7]dodecane (25). A similar reaction series converted 1-benzoyloctamethylenimine (34) into the iminium salt (41). © 1968, American Chemical Society. All rights reserved.