Kinetics and mechanism of iodocyclization reaction of 3,7-dimethylenebicyclo [3.3.1] nonane

Experimental and theoretical studies on the transannular cyclizations of 3,7-dimethylenebicyclo[3.3.1]nonane with polyfluoroalkyl radicals

“…Convenient and selective preparations of functional derivatives of adamantane and noradamantane are based on transannular cyclizations of bicyclo[3.3.1]nonane dienes with electrophilic or radical agents [16][17][18][19][20][21][22][23][24]. It has been shown previously, that transannular cyclizations of polyunsaturated bicyclo[3.3.1]nonane derivatives with electrophiles (iodine, bromine, acids, NHlgS (Hlg = Cl, Br, I), 1-chloromethyl-4-fluoro-1,4-diazoniabicyclo[2.2.2]octane bis(tetrafluoroborate)) [16][17][18][19][20] lead to adamantane derivatives. In contrast, noradamantane, and adamantane derivatives, are formed in the reactions with radical agents (CCl 4 /AIBN, CHCl 3 /g-irradiation, C 6 H 5 SH, CH 3 PhSO 2 Hlg (Hlg = Cl, Br)) [21][22][23][24].…”

“…Adamantyl and noradamantyl moieties are often used as the building blocks for new drugs with antiarrhythmic, hypoglycemic, antiviral and other types of physiological activity [11][12][13][14][15]. Convenient and selective preparations of functional derivatives of adamantane and noradamantane are based on transannular cyclizations of bicyclo[3.3.1]nonane dienes with electrophilic or radical agents [16][17][18][19][20][21][22][23][24]. It has been shown previously, that transannular cyclizations of polyunsaturated bicyclo[3.3.1]nonane derivatives with electrophiles (iodine, bromine, acids, NHlgS (Hlg = Cl, Br, I), 1-chloromethyl-4-fluoro-1,4-diazoniabicyclo[2.2.2]octane bis(tetrafluoroborate)) [16][17][18][19][20] lead to adamantane derivatives.…”

Selective transannular cyclization of 3,7-bismethylenebicyclo[3.3.1]nonane with F-TEDA-BF4 in protic solvents

“…4b: colourless oil. 1 H NMR, d: 0.85 (s, 3H, CMe), 1.15 (t, 3H, CH 2 Me, J 6.9 Hz), 1.30-2.22 (m, 14H, Ad), 3.47 (q, 2H, OCH 2 , J 6.9 Hz).…”

“…1 H NMR, d: 1.40-2.35 (m, 14H, Ad), 3.30 (s, 3H, 3b: colourless oil 1. H NMR, d: 1.17 (t, 3H, Me, J 6.9 Hz), 1.3-2.4 (m, 14H, 3c: colourless oil 1.…”

“…1 H NMR, d: 1.40-2.35 (m, 14H, Ad), 3.30 (s, 3H, 3b: colourless oil 1. H NMR, d: 1.17 (t, 3H, Me, J 6.9 Hz), 1.3-2.4 (m, 14H, 3c: colourless oil 1. H NMR, d: 1.11 (d, 6H, 2Me, J 6.3 Hz), 1.43-2.3 (m, 14H, 3d: white crystals, mp 123-125.5 °C.…”