Quaternary carbon centers represent important organic structural motifs that are ubiquitous in natural products, pharmaceutical molecules, and functional materials. The rational introduction of quaternary carbon centers into drug candidates can significantly improve their biological activity, target selectivity, and metabolic stability. Accordingly, the efficient construction of quaternary carbon centers has emerged as a major research focus in the fields of organic synthesis and medicinal chemistry. Nevertheless, the efficient synthesis of quaternary carbon centers remains a significant challenge, owing to their substantial steric hindrance and propensity for elimination or other side reactions. Consequently, there is an urgent need for the development of milder and more efficient synthetic methodologies. Heteroarenes serve as the core scaffolds in pharmaceutical molecules, functional materials, and natural products. The efficient synthesis and structural modification of heteroarenes and their derivatives have long been a research hotspot in organic chemistry. The Minisci reaction is a type of organic reaction that involves the radical addition of nucleophilic carbon radicals to protonated electron-deficient heteroarenes, allowing the introduction of various functional groups such as alkyl and acyl groups into the heteroaromatic frameworks. This transformation has been widely used in medicinal chemistry and organic synthesis, playing a crucial role in drug discovery, total synthesis of natural products, and the creation of functional materials. Notably, the Minisci reaction also represents an important strategy for constructing quaternary carbon centers. By enabling the direct addition of carbon radicals to heteroarenes, this reaction allows quaternary carbon structures to be incorporated into heteroaromatic systems, providing a practical synthetic route. In view of the above, this review presents a systematic summary of recent advances in the construction of quaternary carbon centers via the Minisci reaction, with particular emphasis on the diversity of radical precursors that have been successfully employed. These include carboxylic acids and their derivatives, borates, alkenes, alkyl halides, alkanes, alcohols and their derivatives, and aldehydes. For each class, the underlying reaction mechanisms, representative reaction conditions, substrate scopes, and limitations are critically evaluated, with the goal of providing both a comprehensive reference for synthetic chemists and a perspective on the challenges and opportunities that lie ahead.

Key words: quaternary carbon centers, Minisci reaction, radical transformation, heteroarenes