Reduction Alkylation And Cycloaddition Reaction Of Chlorosilanes

The development and comprehensive application of transition metal catalyzed reduction coupling reaction of carbon electrophiles provide a new strategy for the construction of carbon-carbon/carbon hybrid bonds,the strategy well solved the existing in nucleophile reagents(prefabrication of metal reagents,the compatibility and stability of functional groups are limitedand,use of strong acids and bases),thus effectively broadening the compatibility of functional groups and reducing economic costs,and has broad development prospects.For the silyl electrophilic reagents research provides a new opportunity.However,silyl electrophiles have higher bond energies and larger bit groups due to the influence of silicon atom radius and electronegativity.As a result,ordinary silyl electrophiles are rarely used in reductive coupling reactions.In addition,by the method of reductive coupling reaction,it has been reported in the strategy of constructing carbon ring for silyl cycloaddition of electrophilic reagent has been seldom developed.This paper studied the nickel catalyzed silyl electrophilic reagent alkylation under reductive coupling system coupling and silyl cycloaddition reaction,main content includes the following four parts:Ⅰ.First of all,we review the strategy of C-Si bond in detail.Subsequently,the progress of transition metal catalyzed reactions from the perspectives of coupling reactions involving silyl electrophiles and the construction of silyl cyclic compounds.Finally,we summarize and outlook on the two aspects of the research.Ⅱ.We have successfully realized the reductive coupling reaction between ordinary chlorosilane and α-bromophosphine/sulfone,by optimizing reaction conditions.The reaction substrate has a wide range of application and good functional group compatibility.Through a series of mechanism verification tests,we put forward the mechanism of in-situ nucleophilic substitution reaction of metal reagent SN2.Ⅲ.We applied 1,1-dichlorosilane and diene as substrates to the reduction coupling system,and successfully realized the first reduction coupling reaction of 1,1-dichlorosilane [4+1] cycloaddition.The work also realized the construction of silicon instead of screw ring and explored the optical properties.We have verified the reaction mechanism preliminarily and put forward the reaction mechanism of silicochlorine activation participating in the reaction first.Ⅳ.We further explored the reduction coupling reaction of 1,2-dichlorosilane and diene,and successfully realized the [4+2] cycloaddition reaction of 1,2-dichlorosilane through ligand improvement.This reaction has better functional group compatibility,but the reaction is only applicable to diene with π system,so there are some limitations.We successfully oxidize the target product,which can efficiently construct a seven-membered ring.