Highly efficient, selective, and direct C–H peroxidation of 9-substituted fluorenes has been achieved using a Mn–2,2′-bipyridine catalyst via radical–radical cross-coupling. Moreover, this method effectively promotes the vicinal bisperoxidation of sterically hindered various substituted arylidene-9H-fluorene/arylideneindolin-2-one derivatives to afford highly substituted bisperoxides with high selectivity over the oxidative cleavage of C═C bond that usually forms the ketone of an aldehyde. Furthermore, a new approach for the synthesis of (Z)-6-benzylidene-6H-benzo[c]chromene has been achieved via an acid-catalyzed skeletal rearrangement of these peroxides. For the first time, unlike O–O bond cleavage, reductive C–O bond cleavage in peroxides using the Pd catalyst and H₂ is described, which enables the reversible reaction to afford exclusively deperoxidized products. A detailed mechanism for peroxidation, molecular rearrangement, and deperoxidation has been proposed with preliminary experimental evidences.

中文翻译：

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锰催化的季铵盐的合成：在催化过氧化和重排反应中的应用。

使用Mn-2,2'-联吡啶催化剂通过自由基-自由基交叉偶合，实现了9-取代芴的高效，选择性和直接CH-H过氧化。而且，该方法有效地促进了空间受阻的各种取代的亚芳基-9 H-芴/芳基吲哚-2-酮衍生物的邻位双过氧化，从而提供了高取代度的双过氧化物，其对通常形成环戊二烯酮的C═C键的氧化裂解具有高选择性。醛。此外，一种合成（Z）-6-亚苄基-6 H-苯并[ c的新方法通过这些过氧化物的酸催化的骨架重排已经获得了] 1，1-二烯。与O-O键断裂不同，这是首次描述了使用Pd催化剂和H ₂在过氧化物中进行还原性C-O键断裂，这使得可逆反应可提供完全脱氧的产物。已经提出了过氧化，分子重排和脱过氧化的详细机理，并提供了初步的实验证据。