Chapter 9: Reactions of Organophosphorus and Organosilicon Compounds

The mechanistic pathways underlying these transformations are detailed, with emphasis on how reaction conditions and reagent structure influence the formation of E or Z alkene isomers. The chapter then shifts focus to organosilicon compounds, including silyl enol ethers and vinylsilanes, exploring how silicon substituents function as both activating groups and protective units in synthesis. Silicon's ability to stabilize reactive intermediates and direct reactivity toward specific regiochemical outcomes forms a central theme throughout the chapter. The Peterson olefination is presented as a silicon-based alternative to phosphorus-mediated olefination, illustrating parallel synthetic strategies. Additional coverage addresses how trialkylsilyl groups facilitate regiochemically selective transformations and how the Tamao-Fleming oxidation enables conversion of carbon-silicon bonds into carbon-oxygen bonds, ultimately yielding alcohols or related functional groups. Together, these methodologies demonstrate how main-group organometallic chemistry enhances chemoselectivity, regioselectivity, and stereochemical control in multistep synthesis.