Polychlorinated hydrocarbons are particularly important in organic synthesis and chemical industries, especially in the fields of pharmaceuticals and materials, which have attracted wide attention of chemists and given birth to various methods for the synthesis of chlorinated organic compounds. The introduction of polychloroalkyl can be used as key component to change the drug activity of the compound. At the same time, polychloroalkyl can be used as precursors to transform into aldehydes, ketones, carboxylic acids and other functional groups with different functions, providing strong support for the realization of late synthesis and modification of natural products. The strategy of constructing polychlorinated compounds by breaking C—H bonds in polychloroalkanes has become a hot research topic among chemists due to its high step economy and has made significant progress in research. In this paper, the use of dichloromethane and trichloromethane as precursors of polychloroalkyl is summarized, starting from different reaction systems (transition metal catalyzed, visible light mediated, metal-free involved), the relevant work of polychloroalkylation reactions based on C—H bond breaking strategy in the last decade is reviewed, and the reaction design, mechanism research, and research prospects are reviewed.

Key words: polychlorinated alkylation, chlorinated alkanes, radical reaction, C—H bond cleavage