Silylated Cyclohexadienes: New Alternatives to Tributyltin Hydride in Free Radical Chemistry

Total Synthesis of Leucascandrolide A

“…Reductive deselenylation of 23 to 24 (80 %) was achieved under tin-free conditions with the silylated 1,4-cyclohexadiene reagent recently developed by Studer and Amrein. [25] Following ester hydrolysis with TMSOK, seco acid 25 was obtained. Our objective at this point in the synthesis was to differentiate the two secondary hydroxy groups at C9 and C17 through a regioselective macrolactonization reaction.…”

Synthesis and Structural Characterization of Isomeric Bis[3,4,5,6-tetrakis(trimethylsilyl)cyclohexen-1-yl]dimethoxysilanes

“…[15][16][17][18][19] Although the strategy of Birch type reductive silylation has several drawbacks vs electrochemical silylation such as using metal reducing agents, and irregular yields, it has been well developed as one of useful methods for the formation of carbon-silicon bonds in both carbon and organosilicon chemistry. [20][21][22][23][24][25] Reductive polysilylations of PhSiCl3 and PhMeSiCl2 were reported to occur with excess lithium and Me3SiCl in THF to yield tetrasilylated cyclohexene (Ttc = tetrakis(trimethylsilyl)cyclohex-1-ene) derivatives. 7,8,11 However, to our knowledge, no investigation for the synthesis of a compound having two Ttc substituents on the same silicon atom has been appeared.…”

On the Scope of Radical Reactions Utilizing InCl3/coreductant as an Efficient Reagent for Synthetically Useful Transformations in Aqueous and Organic Solvents

“…Several promising and valuable alternatives have been found and utilized over the years TMS 3 SiH [7,12], cyclohexanedienyl-silane [8], tri-2-furanylgermane [9], Schwartz reagent [10,11] and gallium hydride [11] have been reported but their application has not extended beyond that of Bu 3 SnH in various organic solvents. Recently, the reports by others and us on the use of TMS 3 SiH and quaternary ammonium salts of phosphinic acids as chiral and achiral hydrogen donors have opened the avenue for further utilization of the previously reported InCl 3 /coreductant as a potential environmentally benign and versatile hydrogen donor system, which is able to sustain a broad range of free radical transformations [13,14,15,16].…”