Efficient organic reactions and polymerizations by use of organosilicon reagents

New chemistry on the following efficient chemical transformations is described in this dissertation. Reaction of primary nitro compounds sequentially with KH and Me{dollar}sb3{dollar}SiSSiMe{dollar}sb3{dollar} in THF gave thiohydroxamic acids in 56-92% yields. For these reactions, the resulting thiohydroxamic acids can be desulfurized by light in situ to produce nitriles in 78-87% yields. Furthermore, treatment of primary nitro compounds with MeSSiMe{dollar}sb3{dollar} or PhSSiMe{dollar}sb3{dollar} under alkaline conditions afforded thiohydroximates in 61-78% yields. Also, a variety of secondary nitro compounds were reacted with KH and Me{dollar}sb3{dollar}SiSSiMe{dollar}sb3{dollar} or MeSSiMe{dollar}sb3{dollar} in THF to give oximes in 68-96% yields. In all of these reactions, the thiosilanes acted as "counterattack reagents."; An efficient way was developed for the protection of diols by use of MeC(OSiMe{dollar}sb3{dollar}) = NSiMe{dollar}sb3{dollar}. Various diols were treated with MeC(OSiMe{dollar}sb3{dollar}) = NSiMe{dollar}sb3{dollar} under alkaline conditions to give the corresponding disilyl ethers in 60-95% yields. On the other hand, a new procedure was developed for the removal of two methyl groups from aryl methyl ethers. Aryl methyl ethers containing two methoxy units were treated with {dollar}sim{dollar}2.5 equiv of Me{dollar}sb3{dollar}SiSNa in 1,3-dimethyl-2-imidazolidinone at 185{dollar}spcirc{dollar}C in a sealed tube to afford the corresponding aryl alcohols in 78-96% yields after aqueous workup. In these protection and deprotection, MeC(OSiMe{dollar}sb3{dollar}) = NSiMe{dollar}sb3{dollar} and Me{dollar}sb3{dollar}SiSNa behaved as "counterattack reagents."; Also, secondary nitro compounds were converted to ketones under alkaline conditions by use of a catalytic amount of Me{dollar}sb3{dollar}SiCl. The yields ranged from 62-90%. This newly developed organic reaction was then applied to the synthesis of poly(1,3-diketones) from poly(nitroalkenes).; Finally, the concept of "counterattack reagents" was utilized to the synthesis of polymers. Reaction of (MeO){dollar}sb3{dollar}P = O with N(SiMe{dollar}sb3)sb3{dollar} (nonamethyltrisilazene) in THF under alkaline conditions gave a unprecedented silicon-containing polyphosphazene. Reagent N(SiMe{dollar}sb3)sb3{dollar} acted as a "counterattack reagents" in this polymerization.