Alkylphosphinites as Synthons for Stabilized Carbocations.

We present a new acid-free method for the generation of carbocations based on a redox condensation reaction that enables S N 1 reactions with a variety of nucleophiles. We utilize readily synthesized phosphinites that are activated by diisopropyl azodicarboxylate to form betaine structures that collapse upon adding a pronucleophile, thereby yielding reactive carbocation intermediates. We also employ this approach for the alkylation of some bioactive molecules.