In this regard, the modern radical-mediated chemistry has opened up exciting possibilities for transformations and applications in synthesis. One notable avenue explores the visible-light-induced organic photochemical [2+2]-cycloaddition reactions through energy-transfer (EnT) pathways, which result in the formation of fourmembered rings (Figure ). Within this context, a few methods have been well-documented for efficiently producing boryl-substituted cyclobutanes. It is worth mentioning that photochemical [2+2]-cycloadditions operate by energy transfer from an excited state sensitizer to the alkene not bearing the boron, is a wellestablished method. Conversely, [2+2]-cycloaddition reactions that operate by energy transfer to the alkenylboronate 1' are in the early stages of development (Figure ). In fact, Watson and Gilmour demonstrated, in 2018, the feasibility of energy transfer to alkenylboronates, particularly in the context of alkene isomerization reactions. However, Brown has elegantly developed the pioneering work of [2+2]cycloaddition reactions that operate by energy transfer to the alkenylboronate 1' which is typically an electron deficient alkene (Figure ). Inspired by these elegant prior art works, we envisioned that polyborylated cyclobutane could be constructed through [2+2]-cycloaddition reactions of olefins with polyborylated alkenes (Figure ). Polyborylated alkenes (1,4, and 6), which comprise molecules with more than one single C-B bond, serve as valuable polymetalloid reagents in contemporary organic synthesis, facilitating a broad range of transformations that encompass the construction of multiple C-C and C-heteroatom bonds, through boron-selective transformations. However, their chemoselective reactions on the electron deficient double bond moiety have recently attracted research interest since they provide an efficient and flexible platform to construct complex molecular diversity (Figure ). Our group, and others, successfully utilizing these polyborylated alkene motifs in the context of addition-reactions such as the Diels-Alder and the cyclopropanation reactions (Figure ). Moreover, we recently explored the use of gem-diborylalkenes as radicalreactive groups for the first time (Figure ). These methods exploit a photoredox decarboxylative/deoxygenative radical addition to gem-diborylalkenes to afford α-gem-diboryl carbon-centered radicals (Figure ). These radicals' (V, V', and V'') benefit from additional stability by virtue of an interaction with the empty p-orbitals on borons, ultimately offering an efficient and broadly applicable pathway to afford 1,1-bisborylalkanes and β-keto-gem-diborylalkane respectively (Figure ). However, in these photo-redox mediated scenarios, the gem-diboryl radical (V, V', and V'') experiences a rapid single electron transfer, transforming it into the stabilized gem-diboryl anion (IV, IV', and IV''), which subsequently becomes trapped by a proton (Figure ). These events hinder our ability to introduce different electrophiles than a proton or deuterium, at the gem-diborylcarbon position via single electron transfer (SET). We anticipate that this limitation can be overcome by eliminating the use of proton sources like carboxylic acids and generating this radical through processes other than SET. We hypothesized that this can be achieved by visible-light-induced photochemical [2+2]-cycloaddition reactions pathways that can operate by EnT to the polyborylated alkenes 1, 4, and 6 (Figure ). This approach would enable the insitu generation of polyborylated biradical intermediates I-III for the very first time. These intermediates could then be coupled with olefins, ultimately leading to the construction of distinctive polyborylated cyclobutane motifs (Figure ). However, there are several potential challenges associated with these reactions, including: