The developments of the living alkene polymerization method have achieved great progress and enabled the precise synthesis of important polyalkenes with controlled molecular weight, molecular weight distribution, and architecture through an anionic, cationic or radical strategy. However, it is still challenging to develop a living alkene polymerization method through an all-in-one strategy where anionic and radical characteristics are merged into one polymerization species. Here, a versatile living polymerization method is reported by introducing a well-established all-in-one covalent-anionic-radical Barbier strategy into a living polymerization. Through this living covalent-anionic-radical Barbier polymerization (Barbier CARP), narrow distributed polystyrenes, with Đ as low as 1.05, are successfully prepared under mild conditions with a full monomer conversion by using wide varieties of organohalides, for example, alkyl, benzyl, allyl, and phenyl halides, as initiators with Mg in one pot. This living covalent-anionic-radical polymerization via a Barbier strategy expands the methodology library of polymer chemistry and enables living polymerization with an unconventional polymerization mode.

To develop novel polymerizations capable of manipulating low molecular weight distribution (Đ) through novel polymerization species rather than radical, anionic, or cationic species is highly desirable and challenging, which will enable polymer chemistry with a new polymerization mode and synthetic route. Grignard reagent mediated alkene polymerization is generally regarded as anionic polymerization that is not applicable for nonpolar monomers like styrene (St). Here, the turbo-Grignard reagent mediated polymerization of St is demonstrated to exhibit intriguing all-in-one characteristics of covalent–anionic–radical polymerization. Under mild conditions, polystyrenes with narrow molecular weight distribution can be obtained with over 99% monomer conversion by using a series of turbo-Grignard reagents (RMgX·LiCl) as initiators, including alkylMgCl·LiCl, BnMgCl·LiCl, and allylMgCl·LiCl. In comparison with traditional Grignard reagent mediated reactions and polymerizations exhibiting zero tolerance with reactive hydrogen, this turbo-Grignard reagent mediated polymerization exhibits compatibility with reactive hydrogen under mild conditions and expands the library of polymerization with an intriguing turbo-Grignard reagent mediated all-in-one covalent, anionic, and radical polymerization mode.