A methylene group inserted between proximal carbonyl groups underwent exclusive oxyfunctionalization with sodium chlorite in the presence of redox‐inert Hf^IV in water. Direct oxidation methods have conventionally suffered from manifold side reactions such as oxidative fragmentation, dimerization, and overreactions, together with the use of toxic and intractable oxidants. Although alternative routes involving prior α‐functionalization can be executed under mild conditions, preparatively valuable oxidation methods that deliver high levels of both conversion and selectivity remain a prized goal from the standpoint of streamlining organic synthesis. Chlorine dioxide, which was generated as a yellowish gas during the reaction, is considered to be a bona fide oxidant against active methylene compounds. The pivotal role of water was clear, given that the reaction was significantly retarded in both aqueous acetonitrile and ethanol, which can solubilize sodium chlorite.

中文翻译：

---

使用亚氯酸钠在水中对活性亚甲基化合物进行氧官能化

在存在氧化还原惰性Hf ^IV的情况下，使用亚氯酸钠对插入在近端羰基之间的亚甲基进行专有的氧官能化在水里。传统上，直接氧化方法会遭受多种副反应，例如氧化裂解，二聚反应和过度反应，以及使用有毒和难处理的氧化剂。尽管可以在温和的条件下进行涉及先前α-官能化的替代路线，但从简化有机合成的角度来看，提供高水平转化率和选择性的制备上有价值的氧化方法仍然是一个值得追求的目标。在反应过程中以淡黄色气体形式生成的二氧化氯被认为是对抗活性亚甲基化合物的真正氧化剂。水的关键作用是明确的，因为该反应在乙腈水溶液和可溶解亚氯酸钠的乙醇中均明显受阻。