Study On The Cross-coupling Reaction Of N-acyliminium Ions With Olefins And Cyloaddition Reaction With Alkynes

The thesis consists of three parts.In the first part, the formation, the reactions and the application of N-acyliminium ions in organic synthesis have been reviewed. The influencing factors to the reaction of N-acyliminium ions have also been introduced.In the second part, a concise synthesis of3-(1-alkenyl) isoindol-1-one and5-(1-alkenyl)pyrrol-2-one by the intermolecular cross-coupling reaction of N-acyliminium ions which produced from dehydroxylation N-benzyl-3-hydroxyisoindol-1-one (or N-methyl-3-hydroxyisoindol-1-one, N-hydro-3-hydroxyisoindol-1-one, N-benzyl-5-hydroxypyrrol-2-one, N-methyl-5-hydroxypyrrol-2-one), with unactivated olefins (styrene,1,1-diphenylethylene, a-methylethylene, indene, cyclohexene,3,4-dihydrop-yran,2,3-dihydrofuran,1-hexene) catalyzed by BF3-OEt2has been established. For most of the olefins, the expected Csp3-Csp2cross-coupling products have been afforded, but unfavored for the a-methylstyrene and1-hexene; the Csp3_Csp3cross-coupling products were obtained.In the third part, a concise synthesis of13-aryl-5H-benzo[5,6]azepino[2,1-a]-isoindol-7(11bH)-one by cycloaddition of N-acyliminium ions, produced from dehydroxylation of N-benzyl-3-hydroxyisoindol-1-one, with unactivated alkynes (phenylacetylene,4-chlorophenylacetylene,4-methylphenylacetylene,4-methoxy phenylacetylene, ethylphenylpropiolate,1-phenylpropyne) catalyzed by BF3-OEt2has been established. The substituent effect to the reaction is studied by the comparasion of the cycloidition reactions of N-(3-nitrobenzyl)-3-hydroxyisoindol-1-one (or N-(3-chlorobenzyl)-3-hydroxyisoindol-1-one, N-(3-methylbenzyl)-3-hydroxyisoindol-1-one, N-(3-methoxybenzyl)-3-hydroxyisoindol-1-one) with phenylacetylene at the same conditions. Enantioselectivity of the cycloaddition reactions of (R) N-(α-methylbenzyl)-3-hydroxylisoindol-1-one with unactivated alkynes (phenylacetylene,4-chlorophenylacetylene,4-methylphenylace-tylene,4-methoxyphenylacetylene) has aslo been investingated.