Study On Environmentally Friendly Barbier-Type Reaction

In recent years, with the rapidly emerging and development of green chemistry, environmentally friendly-economics have become an important impetus of technology innovator, and make green organic synthesis face serious challenge. Developing more benign synthetic procedures in chemical synthesis is important in moving towards sustainable technologies. In reducing the amount of waste, energy usage, and the use of volatile, toxic and flammable solvents, several approaches are available including avoiding the use of organic solvents for the reaction media. Replacement media include non-volatile and recyclable ionic liquids, H2O, supercritical CO2, polyethylene and polypropulene glycol. An alternative approach avoids the use of a reaction medium as the so-called 'solvent free' or 'solventless' reaction.Being important building blocks and versatile synthons, homoallylic and homopropargyl alcohols are highly featured in the organic syntheses of many biological active molecules such as macrolides, polyhydroxylated natural products, and polyether antibiotics. Among the existing means to construct these synthetically and biologically important molecules, metal-mediated allylation and propargylation is one of the easiest and most convenient. Since the 1980s, it has been gradually realized that carbonyl allylation can even be achieved in aqueous media through a Barbier-type reaction. This discovery attracts considerable attention because of the increasing public interest in green chemistry. So far many metals have been reported to be effective in mediating the coupling between organic halides and carbonyl compounds to give the corresponding alcohols in aqueous media. However, these reactions involved the use of waters -either alone or with co-solvent- as a medium for reactions with organic or organometallic reagents.From the view of environmentally friendly, this thesis achieved the solvent-free synthesis of homoallyl and homopropargyl alcohols through zinc-mediated Barbier-Type reaction. At the same time, the addition reaction of organozinc reagent and ketones was investigated.