Aspects of functionalisation at saturated carbon centres

Nott, Andrew Philip (1980) Aspects of functionalisation at saturated carbon centres. University of Southampton, Doctoral Thesis.

Abstract

The oxidation of saturated hydrocarbons by metal salts, a subject of industrial importance, has been reviewed. Results are presented for adamantane, a series of bridged hydrocarbons, cycloalkanes and n-alkanes. Lead (IV) and periodic acid selectively Save bridgehead substituted derivatives with adamantane, bicyclo[3.3.1.1 nonane and bicyclo[3.2.2.] nonane in high yield but showed low reactivity towards strained systems. With silver peroxide lower conversions of hydrocarbons to oxidation products were obtained and lower selectivity for attack at tertiary carbon centres relative to secondary centres was observed. The more strained hydrocarbons were not only less reactive, but were less selectively oxidised by lead (IV), periodic acid and silver peroxide. Chromium (VI) and potassium permanganate gave high consumptions with all substrates, but displayed little selectivity and gave low yields of products. Permanganate oxidation was accompanied by a novel rearrangement, the conditions for which led to the postulate that Mn03+ was the effective oxidant. The literature concerning the synthesis of bridged heterocyclic annulenes is reviewed. The condensation of 4,6-dimethylbicyclo[3.3.1.] nona-3,6-diene-2,8-dione with some vicinal diamines is described. Detailed studies of spectral and chemical properties of the resulting 1,4-diazepines were made. The significance of homoaromaticity within these compounds is analysed. Oxidative methods for the transformation of the methyl groups in diazepines into aldehyde functions are presented. Subsequent attempts to elaborate the aldehydes into bridged heterocyclic annulenes are outlined.

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