Mechanism of transannular bromination reactions of diolefins of the bicyclo[3.3.1]nonane series

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.…”

Synthesis of 1,2-Disubstituted Adamantane Derivatives by Construction of the Adamantane Framework

“…The exposure of starting materials 28 to bromine or iodine forms a charge transfer complex 29 by attacking the less substituted methylene group, due to stereo-electronic factors, followed by synchronous cyclization to form the stable 1-adamantyl cation ion pair 30, leading to the products 31. Reactions were not carried out for preparative purposes; therefore, no yields were reported [56,57]. Scheme 8.…”

Different routes for the construction of biologically active diversely functionalized bicyclo[3.3.1]nonanes: an exploration of new perspectives for anticancer chemotherapeutics

“…156 Apart from the syntheses of these heteroadamantyl systems, the transannular cyclization of appropriately substituted bicyclo [3.3.1]nonanes promoted by electrophiles such as bromine and iodine is also well documented. [255][256][257][258] The contribution of Serguchev and coworkers in this regard is remarkable. During the beginning of this century, his team unveiled their preliminary report on the reaction between 1-chloromethyl-4-uoro-1,4diazoniabicyclo[2.2.2]octane bis(tetrauoroborate) (F-TEDA-BF 4 ) (529) with 3,7-bismethylenebicyclo[3.3.1]nonane (528).…”