Photo-induced Cycloaddition Reactions Of Bicycloalkylidenes With1,4-naphthoquinone And Its Derivatives

Photo-induced reaction as a important part of organic synthesis had made many breakthroughs during the past decades. The main purpose of this dissertation is to investigate photo-induced reactions of2-substituted or2,3-disubstituted-1,4-naphthoquinones with bicycloalkylidenes including bicyclopropylidene, bicyclohexylidene and cyclopropylidenecyclobutane to construct special polycyclic and spirocyclic framework. The main work included in this dissertation is described in the following three parts:1. Photo-induced reactions of symmetrical bicycloalkylidenes with the derivatives of2-substituted-1,4-naphthoquinone were investigated. Except for the conventional products derived from the [2+2] photo-induced cycloaddition of C=C, other rearranged products were also obtained in the photoreactions between bicyclopropylidene and2-substituted-1,4-naphthoquinone derivatives. The basic mechanism of the form of rearranged products was inferred. Photoreactions of bicyclohexylidene with he derivatives of2-substituted-1,4-naphthoquinone were also give the normal [2+2] cycloadducts and only a little rearranged products. For the steric hindrance effect of bicyclohexylidene, the reactions displayed low conversion rates and low yields. 2. Photo-induced reactions of bicyclopropylidene with derivatives of naphtho[2,3-b]furan-4,9-dione were investigated. Becauce of the differance of substituents on furan ring, different [2+2] cycloadducts from different reaction sites on naphtho[2,3-b]furan-4,9-dione and some rearranged products were obtained in these reactions. Some reactions maybe had synthesis prospect for the high yield of the unique product.3. The photoreactions of asymmetrical cyclopropylidenecyclobutane with the derivatives of2-substituted-1,4-naphthoquinone. All the cycloadditions were involved the C=C on naphthoquinones to gave the cyclobutane products and the further rearranged products.