STEREOCHEMISTRY IN LONG-CHAIN BIRADICAL CYCLIZATION

다국어 초록 (Multilingual Abstract)

The structures of 8-membered azalactone isomers produced from photocyclization of 2-(N,N-dibenzylamino)ethyl benzoylacetate were determined by the X-ray structure analysis to clarify the stereochemical behavior of a 1,8-biradical. The remarkable stereoselectivity in cyclization of the 1,8-biradical to form cis- and trans-isomers of the azalactone was not observed. The ring conformations were boat-chair like and dihedral angles between C$_5$- and C$_6$- phenyl groups were ca 45$\circ$ in the both isomers. The 1,8-biradicals in the transition state for the cyclization would have nearly same boat-chair like conformation and twisted configuration with the dihedral angle of ca 45$\circ$ as the corresponding isomer, and this is responsible for luck of stereoselectivity in long-chain biradical cyclization.