KOBAYASHI Kazuhiro Fac. of Engineering, Hokkaido University, 工学部, 助手 (90161976)
ORITO Kazuhiko Fac. of Engineering, Hokkaido University, 工学部, 助手 (20109482)
TOKUDA Masao Fac. of Engineering, Hokkaido University, 工学部, 助教授 (80001296)
1. A conformational dependence of [1,3] sigmatropic photo-rearrangements in , -unsaturated ketones was found by the study of the photolysis of two steroidal 7-membered , -unsaturated ketones.
2. The two new stereospecific rearrangements of excited steroidal oximes were found and mechanisms, which accommodate the stereospecificity of these photo-rearrangements proved by deuterium labelling studies, were proposed.
3. New mothed was devised for two carbon ring expansions of 5- and 6-membered rings of -indanone and - tetralone through the [2+2] photocycloaddition of the enol ethers of the cyclic ketones followed by the radical cleavage of the fused bond of benzohomotropones through [2+2] photocycloaddition of 1- and 2-naphthols with methyl acrylate followed by a -scission of alkoxyl radicals derived from the adducts was also achieved.
4. The photochemistries of cyclic -nitro ketones, 6-membered cyclic , '-dinitro ketones, and cyclic -nitro enones were studied and new photochemical processes of nitro compounds were found.
5. New method was devised on the synthesis of several furanocoumarins and furano quinolones based on the [2+2] photocycloaddition- -scission sequence.
6. Stereo-and regioselective synthesis of cis-1-alky1-2,5-disubstituted pyrrolidines by cyclization of aminyl radicals generated by anodic oxidation of lithium alkenylamides was devised.
7. A simple new general synthesis of marocyclic ketones based on a three-carbon annelation of cyclic ketones followed by the regioselective radical cleavage of the fused bond of the resulting bicyclic systems was devised. New synthesis of 15-membered cyclic ketones, exaltone and ( )-muscone, were achieved by this method.