An organophosphorus redox‐catalyzed method for the direct electrophilic cyanation of C(sp2)–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 PIII/PV=O catalyzed phase transfer activation.

中文翻译：

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通过 PIII/PV=O 催化相转移活化与无机氰酸酯 (OCN–) 进行亲电 C(sp2)–H 氰化


报道了一种有机磷氧化还原催化的 C(sp2)-H 亲核试剂与氰酸钠 (NaOCN) 直接亲电氰化的方法。 OCN-阴离子的催化脱氧官能化是通过使用小环磷环（磷杂环己烷）催化剂与末端氢硅烷O原子受体和丙二酸衍生的溴供体的结合来实现的。单周转条件下的原位光谱表明，不溶性无机氰酸根阴离子通过溴化鏻催化中间体上的溴化物置换而被激活，产生反应性的N结合异氰酸鏻离子，该离子将亲电“CN+”等价物传递给亲核（杂）芳烃和烯烃氧化膦的损失。这些结果证明了通过 PIII/PV=O 催化相转移活化对不溶性无机盐进行脱氧官能化的可行性。