Silver(I)-Catalyzed Insertion Into Si–H Bonds Of Silane With N-nosylhydrazones

Organosilicon compounds are well known to be highly attractive scaffolds and valuable compounds,which have broad applications in organic synthesis,materials chemistry,and pharmaceuticals.Transition-metal-catalyzed such as rhodium,copper,iron,iridium,and silver salts,carbenoid insertion into Si-H bonds with diazo compounds represents a particularly important contribution to synthesize such compounds.Among them,electron withdrawing-group(EWG)-or trimethylsilyl(TMS)-group-stabilized diazo compounds were successfully implemented as carbene precursors in Si-H insertion reactions.However,the utilization of donor diazo compounds in such transformations was not well documented,which significantly limits their further application in organic synthesis.For this reason,the exploration of new strategies and reagents for the rapid assembly of silicon-containing compounds via transition-metal-catalyzed Si-H insertion from unstable diazoalkanes would be highly desirable.On the other hand,sulfonylhydrazones as reliable diazo sources have been widely used in transition-metal catalyzed transformations,particularly in heteroatom-hydrogen insertion reactions such as N-H,O-H,P-H and S-H insertions.To the best of our knowledge,there is no report that demonstrates the direct use of such diazo precursors in Si-H insertions.Promoted by these facts and given the continuous interest in silver catalysis,we envisaged that silver salts could be employed in catalyzing Si-H insertion reactions with N-tosylhydrazones as diazo sources.In this article,we have developed the first practical and efficient silver(I)-catalyzed carbenoid insertion into Si-H bonds with donor diazo compounds generated in situ from N-nosylhydrazones.Moreover,The newly developed method for organosilanes features a broad substrate scope,good functional group tolerance,and the reaction delivers a number of valuable silicon-containing compounds in very high yields(up to 96%).Moreover,organostannanes and organogermanes were as well effectively obtained in very good yields under optimal conditions.