A VERSATILE METHOD FOR CARBON-NITROGEN BOND FORMATION VIA ENE REACTIONS OF ACYLNITROSO COMPOUNDS

Article abstract of DOI:10.1016/S0040-4020(01)93275-2

The use of acylnitroso compounds of the general formula RCONO as enophiles in the formation of carbon-nitrogen bonds is discribed.Both inter- and intramolecular ene reactions have been studied.For the intermolecular examples, nitrosocarbonylmethane, thermally liberated from its Diels-Alder adduct with 9,10-dimethylanthracene, is reacted with variuos olefins giving the corresponding N-alkylhydroxamic acids in moderate to high yields, providing an efficient method for allylic amidation.The regiochemistry of the intermolecular reaction is observed to be the result of kinetic control, and the direction of addition is consistent with attack by the olefin on electron-deficient nitrogen.Several examples of intramolecular ene cyclization are demonstrated, providing efficient entry into both spiro and fused bicyclic nitrogen containing systems which can be viewed as derived from annulation of 5- and 6-membered nitrogen containing ring onto 5- and 6-membered carbocycles, respectively.Various examples of this hetero-annulation scheme are described.Experimental details are also privided describing typical reaction procedures.