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

Radical cyclizations of 3,7-dimethylenebicyclo[3.3.1]nonane with CF3I, n-C3F7I, ICF2COOEt and ICF2PO(OEt)2 selectively led to corresponding 3,7-noradamantanes, which were used for preparation of various polyfluoroalkyl substituted noradamantyl amines and carboxylates. DFT computations revealed that chemoselectivity of the radical cyclizations is realized due to the high electrophilicity of the CF3 radical, as well as due to efficient trapping of intermediate noradamantylmethyl radicals by perfluoroiodoalkane.

Graphical abstractRadical cyclizations of 3,7-dimethylenebicyclo[3.3.1]nonane with RFI selectively led to corresponding 3,7-noradamantanes. DFT computations revealed that chemoselectivity of the cyclizations is realized due to the high electrophilicity of the CF3 radical, as well as due to efficient trapping of intermediate noradamantylmethyl radicals by perfluoroiodoalkane. Figure optionsDownload full-size imageDownload as PowerPoint slide