Amides containing two norbornene fragments. Synthesis and chemical transformations

• Published in: Russian journal of organic chemistry Vol. 40; no. 10; pp. 1415 - 1426
• Main Authors: Kas'yan, LI, Isaev, AK, Kas'yan, AO, Golodaeva, EA, Karpenko, DV, Thrabara, IN
• Format: Journal Article
• Language: English
• Published: NEW YORK Springer Nature 01.10.2004
• Subjects: Chemistry; Chemistry, Organic; Physical Sciences; Science & Technology; SERIES; PARAMETERS; REDUCTION; EPOXIDATION; AZABRENDANES
• DOI: 10.1007/s11178-005-0034-0
• ISSN: 1070-4280

Reactions of stereochemically pure bicyclo[2.2.1]hept-5-en-exo- and endo-2-ylmethylamines with bicyclo[2.2.1]hept-2-ene-5-carbonyl chlorides gave the corresponding carboxamides having two norbornene fragments. Their conformations and steric strains were studied by the MM2 molecular mechanics method, and electron density distribution in their molecules was determined by PM3 quantum-chemical calculations. The results of calculation of the energy of activation for epoxidation of the dienes in the gas phase and in solution (COSMO) showed that chemoselective oxidation of only one double bond therein is impossible. The corresponding diepoxy derivatives were synthesized by oxidation of the dienes with peroxyacetic acid; the oxidation of amides with endo orientation of the carbonyl group was accompanied by heterocyclization with formation of exo-2-hydroxy-4-oxatricyclo[4.2.1.0(3,7)]nonan-5-one. Reduction of the amides and their epoxy derivatives with lithium tetrahydridoaluminate afforded the corresponding secondary amines possessing two cage-like fragments; the reduction products were functionalized at the nitrogen atom by treatment with p-nitrobenzenesulfonyl chloride and p-toluenesulfonyl isocyanate. The structure of the prepared compounds was confirmed by the IR and H-1 and C-13 NMR spectra.