To demonstrate the synthetic utility of the obtained products containing multiple activated sites with prominent and diverse reactivity, compound 3n was converted into a variety of derivatives (Figure ). First, we aimed to elucidate the nature of minor (ca. 10% yield) by-products that emerged during the purification of 3la and similar adducts of benzylidene malononitrile by column chromatography on silica gel. Based on literature precedents, we surmised that the by-products might result from a silicacatalyzed intramolecular aldol-type cyclization. Taking advantage of the observed transformation, we subjected compound 3la to the reaction with trimethylsilyl triflate (TMSOTf) and triethylamine which resulted in TMS-protected cyclopentanol 4a with excellent 95% yield. Likewise, the analogous reaction of 3aa was equally successful and implies that such cyclization could also be performed with other similar cross-coupling products 3. Besides the cyclization reaction, the rich chemistry of malononitrile and carbonyl moieties in 3la also allowed its facile conversion into methyl ester 4b (85% yield) by oxidation with molecular oxygen, synthesis of amide 4c in 65% yield by Cu-catalyzed hydrolysis of a nitrile group, and featured alcohol 4d by reduction with NaBH4. The investigation of the substrate scope revealed that the electrophilic properties of alkenes are crucial for the reaction. Moreover, benzylidene malononitrile 2a, which is quite strong electron acceptor and oneelectron oxidant, could react with cyclopropanol 1a bearing an electron-rich arene moiety even without the catalytic assistance of TBADT catalyst, though the reaction is slower (Table , entry 1 vs 5). This observation can be explained by the formation of a photoactive electron donor-acceptor (EDA) complex between the substrates (Scheme 3). EDA is a molecular aggregate in the ground state, formed by the association of an electron-rich substrate with an electron-accepting molecule. Light excitation results in intramolecular single-electron-transfer (SET) event that occurs within the solvent cage, resulting in the formation of radical cation A and radical anion C. The radical cation A undergoes fast cyclopropane ring opening into β-ketoalkyl radical B which in turn reacts with C producing the cross-coupling products 3. In the reaction with benzylidene malononitrile 2a, cyclopropanol 1a produced 3aa in 25% yield after 3 h of UV light irradiation in acetonitrile. A significantly higher yield of 77% was achieved after 24 h of irradiation. Phenyl cyclopropanol 1g, possessing a less electron-donating aryl moiety, reacted with 2a noticeably slower, resulting in only a 13% yield of 3ga after 3 h. Similarly, the reaction of 1a with less electron-deficient dimethyl fumarate 2f also occurred with reduced rate, yielding 3af in only 16% yield after 19 h. These results stay in line with intermediacy of EDA complexes, which are stronger for more electron-deficient alkenes and for cyclopropanols with more electron-rich aryl moieties.