Photoacetylation of 2-Substituted Adamantanes. Stereochemistry and Substituent Effects

Article abstract of DOI:10.1021/jo00253a033

Photoacetylation of 2-substituted adamantanes with biacetyl gave regiospecifically syn- and anti-4-substituted 1-acetyladamantanes.Competitive reactions for two syn and anti δ-hydrogen abstractions by triplet biacetyl showed that the ρ^* values were -0.50 and -0.79, respectively.The carbon-13 NMR was studied in order to assign stereoisomers.The observed magnitude of the field-effect transmission for two series of substituent effects was understandable on the basis of the geometrical relationships (bond length and angle) between the reaction center and a substituent.