钌催化的16二烯烃关环反应机理研究-study on ruthenium - catalyzed ring closure reaction mechanism of 16 diolefins.docxVIP

ABSTRACT[.(.)‘?丁ransition metal catalyzed cyclization of 1，6-dienes attracted widely interest for its great applic创ion prospect in organic synthesis over the past few years. In this thesis，we have carried out a theoretical investigation at the DFT (B3LYP) level on themechanisms of the ruthenium carbene complexes mediated cycloisomerisation reaction of 1，6…副ene. The model system is formed by 2，2-diallyl dimethyl malonate molecule acting as the 1，6-diene and the [(NHC)Ru=CH2Chl complex which emulates the Grubbs catalyst. Computational study on Ru( 11) catalyzed ring closing metathesis reaction of 1，6，.… diene was reported. 丁he calculations，together with available experimental data，explained the phenomenon that ring closing metathesis reaction occurs 创 low temperature ，but exo-methylene-cyclopentane product wasobtained in the same catalyst at a mùch higher temperature.First ，theoretical research on metathesis between ruthenium carbene and olefin was carried out at DFT (B3LYP) level.The ene咆y barrier of this step comes out to be2.9 kcal/mol. This strongly indicates that the ring closing metathesis reaction theoretically can occur at a low temperature. Besides，transforming paths 仕om the ruthenium carbene catalyst precursorω[ (NHC)RuChl and [(NHC)RuHCI] 时etheoretically sωdied. 丁he most facile path includes formation of a three跚 membered ring through degradation of the ruthenium carbene catalyst. Di旺erent reaction pathways leading to the exo-methylene-cyclopentane product were also studied 什omthe perspective of energy. A generic hydrometallation mechanism ，an oxidativecyclometallation mechanism and a generic allylic C-H insertion mechanism were proposed and calculated with the aid of DFT (日3LYP) method. Our results indicate that the highest energy barrier ofthe hydrometallation route is 25.4 kcal/mo l.And its the most favored reaction channel to obtain the product since it requires theoverω，ming of the lowest activation barrier than