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The acidolysis of 3-endo-azidomethylbicyclo[3.3.1 lnon-6-ene (3) with methanesulphonic acid gave 4-azahomoadamant-4-ene (5) which was also produced from 3-endohydroxymethylbicyclo[3.3.1] non-6-ene (6) on treatment with NaN,-MeS0,H.The formation of (5) was rationalized by a x route cyclization followed by acidolytic ring expansion of intermediate azides on the basis of acidolysis of dideuterioderivatives. The above route was extended to synthesis of 2,2-(1 6) and 7,7-dimethyl-4-azahomoadamant-4-enes (1 7). The acidolysis of 3-endo-azidobicyclo[3.3.1] non-6-ene ( 2 3 ) gave 2-aza-adamantan-anti-4-01 (26) via a x-N+ type cyclization.Organic azides are well-known as excellent synthetic starting materials for various nitrogen-containing organic molecules, although, studies utilizing azide functionalization of carbocycles, particularly, bi-and tri-cycles seem, as yet, to be underdeveloped.2 We have therefore been pursuing attractive synthetic routes to aza-adamantane and related derivatives by utilizing azide functionalization of bi-and tri-carbocycles in order to study their biological proper tie^.^ Previously, we reported convenient and efficient synthesis of 4-azahomoadamant-4-ene and its 5-substituted derivatives by acidolysis and/or photolysis of 2-a~idoadamantanes.~ Here, we report the synthesis of 3-endo-azidomethyl-and -azidobicyclo[3.3.1]non-6-enes and their acidolysis behaviour, the latter providing novel routes to 4-azahomoadamant-4-enes and 4-hydroxy-2aza-adamant ane, respectively .* Eu(fod)3 = tris-(

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Thermolysis of 3‐endo‐azidobicyclo(3.3.1)non‐6‐ene (I) in toluene and subsequent treatment with methanol yield the azatricyclodecene (II) which is methylated to produce the iminium iodide (IV).