Stereoselective dearomatization of benzene, alkylated benzenes and naphthalenes by dihapto-coordination

Chapter 1 is a review of methodologies used for the dearomatization of arenes. It consists of birch reduction and related reductive alkylations, tandem addition reactions of arenes promoted by electron-withdrawing groups or electron-deficient metal fragments, and also the dearomatization reactions of functionalized arenes by using electron-donating substituents or electron-rich metal fragments.; Chapter 2 describes the tandem 1,4-additions to benzene and alkylated benzenes promoted by pentaammineosmium(II). Full characterization and assignments are presented for the 1,4-cis-cyclohexadienes isolated from these reactions and a discussion about the origin of regio- and diasteroselectivity is also provided. Additionally, a novel route to a functionalized benzofuranone is described by using iodolactonization subsequent to the tandem addition.; Chapter 3 includes a brief introduction to the syntheses of arene complexes of TpRe(CO)(MeIm) fragment, along with the dearomatization reactions of benzene and toluene mediated by this metal fragment. A discussion about diastereoselectivity of these tandem additions is presented. It also covers initial studies on the reactivity of TpW(NO)(PMe₃)(η2-benzene) complex.; Chapter 4 is focused on the diastereo- and enantioselective dearomatization of rhenium-bound naphthalenes. It describes four dearomatization reactions: tandem addition, Michael enol cyclization, formal cycloaddition and Michael Michael ring closure. An exploration on tandem addition reactions of TpMo(NO)(MeIm)(η 2-naphthalene) complex is also included.