The strategic replacement of benzene with conformationally rigid and stable C(sp3)-enriched polycyclic scaffolds in small molecules represents an emerging trend in medicinal chemistry. Attributed to their constrained geometries and precisely oriented pendant substituents, these saturated polycycles effectively emulate the topological characteristics of substituted benzenes, which allows for the preservation of desired interactions with biomacromolecules while enhancing the pharmacokinetics, solubility, and metabolic stability of drug candidates. Recent studies have identified 1,2-disubstituted bicyclo[2.1.1]hexanes as potential bioisosteres for ortho-disubstituted benzenes with retained biological activity validated by in vitro experiments. Hence, there is an increasing demand for development of efficient strategies for streamlined access to these bicycles. One of most common methods to construct BCH skeleton is by an intramolecular [2+2] cycloaddition of 1,5-diene under the irradiation of light 3 . Alternatively, an intermolecular cycloaddition of bicyclo[1.1.0]butanes (BCBs) and alkenes is highly desirable since it allows the efficient construction of bicyclic ring through the fusion of two readily available starting materials. Pioneering studies were disclosed by Blanchard 5a in 1966 and De Meijere 5b in 1986. Subsequently, Wipf group 5c reported an intramolecular variant of this cycloaddition under thermal condition in 2006.