Compounds containing heteroatom-heteroatom bonds (X—X bonds) hold extensive application value in fields such as natural products, biotechnology, and materials science. Given the unique role of X—X bonds in regulating molecular bioactivity, the development of efficient strategies for constructing X—X bonds has emerged as an active research direction in organic synthesis. Traditional X—X bond formation predominantly relies on enzymes or metal catalysts to drive reactions, which often results in high costs, cumbersome procedures, and environmental and safety concerns. Moreover, the excessive use of certain toxic reagents significantly restricts their development and application. In such cases, organic electrosynthesis has attracted considerable attention. Compared to traditional approaches, the development of electrosynthesis methods has reduced the use of transition-metal catalysts, thereby significantly improving reaction efficiency and environmental sustainability. With increasing attention and research on the construction methods of heteroatom-heteroatom bonds, the reports on the electrosynthesis of various organic compounds featuring different heteroatoms has become increasingly frequent. In recent years, organic electrosynthesis has gained increasing attention as a green synthetic method, owing to its advantages such as environmental friendliness, high atom economy, and alignment with sustainable development concepts. In organic electrosynthesis, "electrons" serve as redox agents, enabling precise reaction control through modulation of current and voltage. This approach avoids excessive use of external oxidants while simplifying operational procedures, representing a green and efficient strategy for constructing heteroatom-heteroatom bonds. This article focuses on the electrochemical cross-dehydrogenative coupling strategy and takes several common heteroatoms as examples to systematically review a series of electrochemical methods for constructing heteroatom-heteroatom bonds. Given that previous reviews have systematically reported electrochemical methods for constructing N—S bonds, this paper primarily reviews electrochemical approaches for constructing other heteroatom-heteroatom bonds and focuses on introducing the research progress of electrochemical dehydrogenation coupling reactions in constructing X—X bonds. In addition to outlining the relevant reaction mechanisms, we further discuss current challenges and future prospects in this field.

Key words: organic electrosynthesis, heteroatom-heteroatom bond, radical, coupling reaction, hydrogen