New Organic Synthesis based on Photo- and Electrochemical Reactions involving Intramolecular Rearrangements.

1. 通过对两个甾体7元-不饱和酮的光解研究，发现了-不饱和酮中[1,3]异位光重排的构象依赖性。发现了激发的甾体肟的两种新的立体特异性重排，并提出了适应这些被氘标记研究证明的光重排的立体特异性的机制。通过环酮烯醇醚的[2+2]光环加成，-吲哚酮和-四酮的5元和6元环扩展两个碳环，然后通过[2+2]与丙烯酸甲酯的1-萘酚和2-萘酚的[2+2]光环加成，苯并同tropone的熔合键发生自由基裂解，最后由加合物产生的烷氧基自由基也发生了断裂。研究了环硝基酮、六元环酮、'-二硝基酮和环硝基烯酮的光化学性质，发现了硝基化合物的光化学新工艺。基于[2+2]光环加成-裂解序列，设计了几种呋喃香豆素和呋喃喹诺酮类化合物的合成新方法。研究了锂基烯酰胺阳极氧化产生的氨基自由基环化合成顺式-1-烷基1-2,5-二取代吡咯烷的立体选择性和区域选择性。本文设计了一种简单的、新的、基于环酮的三碳环合反应，然后对所得到的双环体系的熔合键进行区域选择性自由基裂解的环酮合成方法。用该方法合成了新的15元环酮，exalone和（）-muscone。

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.