Stereochemistry of the remote oxidative cyanation of methylcyclohexanones

Abstract

1. During the oxidative cyanation of 2-, 3-, and 4-methylcyclohexanones in the Na2S2O8-NaCN system the corresponding 4-cyano(methyl)cyclohexanones are formed regiospecifically. 2. The oxidative cyanation of 2- and 3-methylcyclohexanones takes place diastereoselectively with the formation of trans- and cis-4-cyano-2(3)-methylcyclohexanones in a ratio of 1.5:1 (or 2:1). The selectivity of cyanation is determined by the bridge structure of the intermediate 4-oxo(methyl)cyclohexyl radicals, which are the precursors of the 4-cyanocyclohexanones. © 1989 Plenum Publishing Corporation.