Solvolysis of 1-substituted-2-adamantyl sulfonates. Bridging or no bridging?

Design and synthesis of bioactive 1,2-annulated adamantane derivatives

“…The acid 1 was esterified to the ethyl ester 2, which on treatment with hydroxylamine hydrochloride in the presence of sodium acetate gave the oxime ester 3. Catalytic hydrogenation of 3 over Raney nickel, under different reaction conditions, gave either a mixture of The synthetic route to the pyrrolidine 16 is shown in Scheme 2 and involved ketoacid 12 24 as the starting material, which was esterified to the ketoester 13. Reductive cyanation of 13 was accomplished in high yield using toluenesulphonylmethyl isocyanide (TOSMIC).…”

Stereoselectivity of Destabilized Carbocations: 1-Cyano-2-adamantyl and 3-Cyano-4-protoadamantyl Cations

“…The tresylate of 15 was solvolyzed previously but neither Rearrangement/Solvolysis of exo-4-the stereochemistry nor ion pairing were addressed. [20] The Tosyloxyprotoadamantyl-endo-4-carbonitrile (10c) solvolysis of (ϩ)-14 (ee ϭ 94%) in 60% dioxane required 5 days at 120°C to give 5% of the alcohol 15 with ee ϭ 41%. The reaction of 10c in 60% dioxane at 50°C was monitored by HPLC.…”

“…The solution 153Ϫ154°C. decane-1-carbonitrile (15) [20] , as deHz, 1 H). Ϫ H 4.61, N spectrum of (ϩ)-14 was recorded in the presence of an equimolar 11.32; found C 58.18, H 4.69, N 11.28.…”

“…arrangement of 10c. The mixture was diluted with diethyl ether (15 ml) The volatile products formed from 11c were analyzed by GC (32 (m, 2 H), 1.72Ϫ1.78 (m, 2 H), 1.84 (dddd, J ϭ 12.0/9.5/4.8/1.5 Hz, m OV17, 170°C): 9 (3.0%), 2-adamantanone (24.8%), 15 [20] 1 H), 2.33 (m, 1 H), 2.48Ϫ2.57 (m, 2 H), 2.87 (t, J ϭ 8.2 Hz, 1 H), (18.0%), 17 (see above, 14.5%), 18 (see above, 12.7%), and 22 [22] 7.24 (dd, J ϭ 7.9/1.8 Hz, 1 H). Ϫ 13 C NMR (CDCl 3 ): δ ϭ 30.17 (27.0%).…”

Design and Synthesis of Trypanosoma brucei Active 1‐Alkyloxy and 1‐Benzyloxyadamantano 2‐Guanylhydrazones

“…Each mixture was treated with formic acid to give the corresponding formates via a C2-C3 to C4 metathesis. [12] Saponification of the formates followed by Jones oxidation gave the ketones 22 a,b. Subsequent treatment of 22 a,b with aminoguanidine hydrochloride gave the desired guanylhydrazones 23 a,b.…”