[2 + 1] and [2 + 1 + 1] Cyclization: Diversifying Alkenes for Small Carbocycles via Photocatalytically Accessed 1,3-Dielectrophiles

Small carbocycles such as cyclopropanes and cyclobutanes are widely recognized as key structural motifs in drug discovery campaigns. However, their synthesis remains largely dominated by cycloaddition chemistry, wherein the choice of carbon sources defines the accessible ring size and substitutional diversity. Here, we report a distinct strategy for accessing both cyclopropanes and cyclobutanes from alkenes, enabled by a single-component iodomethylthianthrenium reagent. The key to these transformations lies in harnessing the dual reactivity of photocatalytically generated 3-iodoalkyl thianthrenium to effect size-tunable ring formation. In the presence of a suitable base, a [2 + 1] cyclization is triggered via intermediacy of a thianthrenium ylide. The resulting cyclopropanated linchpin can be readily diversified through diastereoselective C(sp3)–N cross-couplings and a range of radical-mediated functionalizations. In contrast, treatment of the identical 1,3-dielectrophiles with methylene compounds and a milder base switches the reaction mode to a net [2 + 1 + 1] cyclization, selectively furnishing cyclobutanes in a modular fashion. This unified platform not only complements classical retrosynthetic approaches but also enables programmable ring construction that diversifies a common set of starting materials into two distinct small carbocycles.