Electrophilic C(sp2)–H Cyanation with Inorganic Cyanate (OCN–) by PIII/PV=O‐Catalyzed Phase Transfer Activation

An organophosphorus ‐catalyzed method for the direct electrophilic cyanation of C(sp 2 )−H nucleophiles with sodium cyanate (NaOCN) is reported. The catalytic deoxyfunctionalization of the OCN − anion is enabled by the use of a small‐ring phosphacyclic (phosphetane) catalyst in combination with a terminal hydrosilane O‐atom acceptor and a malonate‐derived bromenium donor. In situ spectroscopy under single‐turnover conditions demonstrate that insoluble inorganic cyanate anion is activated by bromide displacement on a bromophosphonium catalytic intermediate to give a reactive N ‐bound isocyanatophosphonium ion, which delivers electrophilic “CN + ” equivalents to nucleophilic (hetero)arenes and alkenes with loss of a phosphine oxide. These results demonstrate the feasibility of deoxyfunctionalization of insoluble inorganic salts by P III /P V =O catalyzed phase transfer activation.