Electrophilic C(sp 2 )-H Cyanation with Inorganic Cyanate (OCN - ) by P III /P V =O-Catalyzed Phase Transfer Activation.
Shicheng HuAlexander T RadosevichPublished in: Angewandte Chemie (International ed. in English) (2024)
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.
Keyphrases
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