Synthesis, Structure, and Derivatives of endo-4-Aminomethyltetracyclo[6.2.1.13,6.02,7]dodec-9-ene

Abstract

Synthesis was performed and structure studied of endo-4-cyanotetracyclo[6.2.1.13,6.02,7]dodec-9-ene prepared by reaction of a stereochemically uniform endo-5-cyanobicyclo[2.2.1]hept-2-ene with cyclopentadiene. By analysis of potential energy surface (PES) for reactions of endo-5-cyanobicyclo[2.2.1]hept-2-ene and the respective exo-stereoisomer with cyclopentadiene (in B3LYP/6-31G(d) approximation) the endo,exo-junction and anti-orientation of the methylene bridges in the bicyclic fragments of the adducts were shown to be preferable. Reduction of the tetracyclic nitrile with lithium aluminum hydride yielded endo-4-aminomethyltetracyclo-[6.2.1.13,6.02,7]dodec-9-ene whose geometry and conformational characteristics were studied by means of molecular mechanics method. Products were obtained from reactions of the tetracyclic amine with p-toluene-, p-chloro-benzene-, p-nitrobenzenesulfonyl chlorides, p-nitrobenzoyl chloride, succinic anhydride, mesityl and p-toluene-sulfonyl isocyanates, phenyl, p-toluenesulfonyl, and benzoyl isothiocyanates, p-nitrophenyloxirane, and N-(2,3-epoxypropyl)carbazole. A series of the amine derivatives was epoxidized with perphtahlic acid. The structure of compounds synthesized was confirmed by analysis of their IR spectra, 1H, 13C, and two-dimensional NMR spectra, and additionally by calculation of the chemical shifts in 1H and 13C NMR spectra by procedures GIAO and CSGT in PBE1PBE/6-31G## approximation.