Preparation of benzoheterocyclic carbaldehydes

ORGN 439

Marek T. Wlodarczyk, mtwlod01@gwise.louisville.edu and Frederick A. Luzzio, faluzz01@gwise.louisville.edu. Department of Chemistry, University of Louisville, 2320 South Brook Street, Louisville, KY 40292
Benzoheterocycles such as benzothiazoles, benzimidazoles and benzoxazoles can serve as unique and versatile scaffolds for experimental drug design as exemplified by the structures of riluzole, ® dabigatran® and flunoxaprofen®. For structural elaboration in lead optimization, the points of attachment can be through a number of individual atoms on either the benzene or heterocyclic rings and may be facilitated through ether, sulfide, amide, amine or carbon-carbon bonds. A scheme for the preparation of aldehydes in the benzothiazole, benzoxazole and benzimidazole series is described. Starting with the corresponding methyl-substituted benzoheterocycle, the conversion entails a two-step sequence. The methyl group serves as the carbon from which the formyl group is derived. Hence, adjustment of the oxidation state of the methyl group first involves a free radical dihalogenation followed by a silver nitrite/dimethylsulfoxide-mediated hydrolysis to the aldehyde functionality. Of special note is the survival of multiple BOC-protected amino substituents on the heterocyclic ring during the entire process. Carbon-carbon forming reactions of the heterocyclic carbaldehydes which are compatible with the multiple BOC protection system will be described along with several types of deprotection reactions.