We report the catalytic reduction of both active esters and amides by selective C(acyl)−X (X=O, N) cleavage to access aldehyde functionality via a palladium‐catalyzed strategy. Reactions are promoted by hydrosilanes as reducing reagents with good to excellent yields and with excellent chemoselectivity for C(acyl)−N and C(acyl)−O bond cleavage. Carboxylic acid C(acyl)−O bonds are activated by 2‐chloro‐4,6‐dimethoxy‐1,3,5‐triazine (CDMT) to form triazine ester intermediates, which further react with hydrosilanes to yield aldehydes in one‐pot two‐step procedures. We demonstrate that C(acyl)−O cleavage/formylation offers higher yields and broader substrate scopes compared with C(acyl)−N cleavage under the same reaction conditions.

中文翻译：

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在氢硅烷存在下通过钯催化的C-O / C-N键裂解获得醛的策略

我们报告了选择性的C（酰基）-X（X = O，N）裂解，通过钯催化的方法获得醛官能团，从而催化活性酯和酰胺的催化还原。氢化硅烷作为还原剂可以促进反应，其收率好至极好，并且对C（酰基）-N和C（酰基）-O键的裂解具有出色的化学选择性。羧酸的C（酰基）-O键被2-氯-4,6-二甲氧基-1,3,5-三嗪（CDMT）活化形成三嗪酯中间体，该中间体进一步与氢硅烷反应在一个锅中生成醛两步过程。我们证明，与在相同反应条件下进行C（酰基）-N裂解相比，C（酰基）-O裂解/甲酰化可提供更高的收率和更宽的底物范围。