An efficient and straightforward phosphine-promoted tandem aza-Michael addition/intramolecular Wittig reaction was developed for the synthesis of polyfunctionalized 2-azetines. After demonstrating that this transformation could be made catalytic in phosphine through in situ reduction of phosphine oxide with phenylsilane, different post-transformation steps have been demonstrated, including an original [2 + 2] photodimerization. Preliminary biological tests highlighted that these fluorinated 1,2-dihydroazete-2,3-dicarboxylates exhibited significant cytotoxicity against the human tumor cell line.