Nickel-catalyzed Carboannulation Reaction Of O-Bromobenzyl Zinc Bromide With Unsaturated Compounds

Indene ring frameworks are present in a large number of biologically active compounds and very useful. Some compounds have shown analgesic and myorelaxation activity, and others are used as valuable intermidiates for synthesis of agents that posses insecticidal properties and the HIV protease inhibitor. Its metallocene complexes are able to catalyze olefin polymerization. Recently, various Pd, Ni and Co catalyzed carboannulation of alkynes with o-halophenyl aldehydes (or ketones) or o-iodophenyl malonates have been used to synthesize indenes, but the disadvantage of these methods is that only internal alkynes could participate in the carboannulation reaction.In this paper, we report a mild preparative method for indenes by Ni(PPh3)2I2 catalyzed carboannulation reaction of o-BrC6H4CH2ZnBr with either internal or terminal alkynes. Acrylates and styrene also undergo the reaction with o-BrC6H4CH2ZnBr to afford indane products. The products have been structurally determined by IR, 1H NMR spectra, 13C NMR spectra, Mass spectra and X-ray crystallography. This thesis includes seven parts as follows.The backgrounds and some relative concepts of this work are briefly introduced. The synthesis methods of the indene ring are concisely reviewed.The Optimized reaction conditions have been found. The reaction was carried out by the addition of 3.5 equiv of Zinc reagent to a solution of 1.0 equiv of substrate and 0.1 equiv of Ni(PPh3)2I2 in CH2Cl2 and stirred 6 h at 40°C.A total of fifteen indenes have been synthesized by o-BrC6H4CH2ZnBr and internal or terminal alkynes. Six of them are new compounds. In these products, the large substituent is in the 2-position of the indene ring and the small substituent is in the 3-position of the indene ring. The regioselectivity can also be proved by the crystal structure of 6f.A total of six indanes have been synthesized by o-BrC6H4CH2ZnBr and acrylates and styrene. Three of them are new compounds. In these products, the large substituent is in the 1-position of the indane ring.The attempt to synthesize multi-rings and macrocycles wasn't successful. We have tried to use 1,3-dibromo-2-phenylprop-1-enes instead of o-BrC6H4CH2ZnBr. But the result isn't perfect. A plausible mechanism based on the experimental results was proposed.The primary investigation of nickel-catalyzed rings expand reaction of the cyclopropane-substituent 4-membered ring was carried out in this paper.