Various benzylidene malononitriles with electron-donating and -withdrawing substituents in the phenyl moiety provided the respective products in 68-86% yields (compounds 3ab, 3ac and 3ad). However, complex reaction mixture and negligible (5-12%) yield of the respective adducts 3 were observed in the reactions with heteroarylidene malononitriles 2n and 2o, as well as with a substrate with a single nitrile group 2p. In addition, no product was found in the reaction of cyclopropanol 1a with methyl-substituted benzylidene malononitrile 2q, which was unreactive under the standard conditions and in the presence of NFSI, probably due to steric hindrance caused by a methyl group. Fumaronitrile 2e, dimethyl fumarate 2f and vinyl phenyl sulfone 2g were alkylated efficiently furnishing the respective products 3ae-ag in 63-85% yields. Notably, products synthesized from alkylidene oxindoles were isolated in good yields (3ah and 3ai, 65% and 66% yield, respectively). Compounds containing an oxindole moiety in their structure have demonstrated a wide range of biological activities. Phenylmaleimide 2j was converted to the corresponding ketone 3aj in good 71% yield. However, similar maleic anhydride 2r was unreactive and only decomposition products of cyclopropanol 1a were observed. Malonate and 1,3-diketone derivatives underwent the desired transformation more sluggish than the rest of the substrates, nevertheless, compounds 3ak, 3al and 3am were isolated in acceptable 44-50% yields. The reaction with less electrondeficient triphenylethylene 2s failed to deliver the corresponding adduct. The evident influence of the electrophilic properties of the alkene indicated that it was not an insignificant bystander in the reaction, merely intercepting the cyclopropanol-derived β-ketoalkyl radical. Instead, it plays a crucial role in the reaction mechanism (see discussion below).