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

1.通过对两种甾体7元，β-不饱和酮的光解研究，发现了[1，3] σ迁移光重排的构象依赖性.发现了两种新的激发态甾体肟的立体专一性重排，并提出了氘标记研究证实的立体专一性重排机制.设计了一种新的方法，通过环酮的烯醇醚的[2+2]光环加成，然后通过1-和2-萘酚与丙烯酸甲酯的[2 +2]光环加成，再通过α-甲基丙烯酸酯的[2+ 2]开环，使苯并同芳酮的稠合键自由基断裂，使-茚满酮和-四氢萘酮的5-和6-元环的两个碳环扩环。同时也研究了加成物中烷氧基的断裂.研究了环硝基酮、六元环二硝基酮和环硝基烯酮的光化学反应，发现了硝基化合物的新的光化学过程。基于[2+2]光环加成-断裂反应，设计了一种新的合成呋喃香豆素和呋喃喹诺酮类化合物的方法.设计了通过阳极氧化烯基酰胺锂产生的胺基自由基环化反应立体选择性和区域选择性合成顺式-1-烷基-2，5-二取代吡咯烷.本文提出了一种简单的新的环酮的一般合成方法，该方法基于环酮的三碳加成，然后通过区域选择性自由基裂解所得到的双环体系的稠合键。用该方法合成了15元环酮-exaltone和（）-麝香酮。

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.