Annulation Of Unsaturated Hydrocarbons With Organosilicon

Silicon is very rich,and its content is second only to oxygen in the earth's crust.Organosilicon compounds are widely used in pharmaceutical molecules,material chemistry,and organic functional materials due to its unique physical and chemical properties.For a long time,chemists have devoted their efforts to the development of organic silicon chemistry to provide fruitful research results.In the past,metal reagents silylation coupling reaction was the most direct method for synthesizing organosilicon compounds.However,the requirement of highly expensive transition-metal catalysts and/or the harsh conditions greatly limited their applications in synthesis.In recent years,both transition metal-catalyzed silylation strategy and oxidative radical silylation strategy have becoming the important and straightforward methods to synthesize organosilicon compounds,which feature good regioselectivity and high atomic economy.This dissertation focuses on the annulation reaction of unsaturated hydrocarbons with silicon reagents,which proceeded through transition metal-catalyzed strategies or oxidative radical strategies for the synthesis of various organosilicon compounds.The dissertation includes five parts:(1)We summarize recent advance of the silylation reaction of silicon reagents and unsaturated hydrocarbons,including oxidative radical silylation reaction of silane and unsaturated hydrocarbons,transition metal-catalyzed silylation reaction of silane and unsaturated hydrocarbons and transition metal-catalyzed silylation reaction of silicon boron reagents and unsaturated hydrocarbons.(2)An iron-catalyzed oxidative radical cyclization reaction of N-aryl alkynamides and silanes was presented.By using ferrous acetylacetonate as catalyst,tert-butyl peroxide as oxidant,a series of potentially biologically active spiro compounds were synthesized with excellent yields under air atmosphere.Control experiments show that the reaction undergone a radical process,and ¹⁸O isotopic tracking experiments verifies the origin of oxygen in the spiro rings.(3)A manganese-catalyzed oxidative radical tandem cyclization reaction of N-arylenamides and silanes was established.Three types of chemical bonds,including C-Si bond,C-C bond and C-N bond,were established by activating Si-H/silyl C(sp3)-H bonds,and a series of six-membered nitrogen-containing silicon heterocyclic derivatives are synthesized.This method provides an efficient way for the construction of nitrogen-containing polycyclic silicon heterocycles.(4)A novel palladium-catalyzed[5+1]carbonylative cyclization reaction of 1,4-enynes and silanes was developed.By using palladium chloride as catalyst,carbon monoxide as carbonyl source,a series of potentially biologically active phenol compounds were synthesized under mild conditions.The reaction features broad substrate scope and good functional group compatibility.Control experiments and ¹³C isotope tracking experiments confirmed that the carbon atom of C-O bond derived from carbon monoxide.(5)A palladium/copper-catalyzed biscarbonylation[5+1]cyclization reaction of1,4-enynes with silicoboron reagents was reported.By using bis(triphenylphosphine)palladium dichloride and copper fluoride as catalysts,trifluorotoluene as solvent,three types of chemical bonds,including C-Cbond,C-O bond and C-Si bond,were constructed in one step under mild conditions,and a series of acetyl silyl phenol compounds were efficiently synthesized.