Given the bespoke reactivity in homodimerization, we next assessed non-symmetrical dienes, containing a geminal BPin, in intermolecular 2+2 cycloadditions (Scheme 3). Subtle modifications enabled reactions to be carried out using 5 equivalents of alkene coupling partner without the necessity of a syringe pump, further underpinning the unique reactivity of the geminal system. The reaction was tolerant to modifications of the diene aromatic ring (18 to 21), generating the cycloadduct in good yield, while incorporation of functionality in the alkene coupling partner was also effective (22 and 23). The protocol was amenable to simple styrene and diene coupling partners affording the syn diastereomer as the dominant product (24 to 26). Intriguingly, in stark contrast to the mono-substituted system 1, electron deficient Michael acceptors were efficient (27). Electron deficient alkenes were compatible with various dienes including electron-rich ( ), electron-poor (29) and heterocycles (30). Moreover, varied alkenes could be employed, including bulkier acrylates (31), acrylonitrile (32) and methyl methacrylate (33). The use of a borylated alkene enabled the synthesis of polyboronate structure (34). The scope culminated in the synthesis of bicyclopentane 35, granting expedient access to a 3D framework containing a Weinreb amide, an alkene, and a geminal boronic ester for further downstream synthetic manipulations.