Ketones serve as one of the most critical building blocks in organic synthesis, involving numerous functional group transformations. Herein, we report an unprecedented photoredox–nickel metallaphotoredox-catalyzed decarboxylative acylation of common aliphatic acids with readily available aromatic and aliphatic thioesters. A wide range of structurally diverse asymmetrical aryl alkyl and dialkyl ketones have been constructed in yields of up to 98% with this strategy. The protocol has excellent reaction selectivity and functional group compatibility, representing a significant step forward in ketone synthesis. The one-pot decarboxylative acylation at the gram scale from two different carboxylic acids and the late-stage application for the synthesis of complex ketones shows its synthetic robustness. Both mechanistic experiments and density functional theory (DFT) calculations suggest that the decarboxylative acylation reaction operates via an underdeveloped Ni(I)–Ni(II)–Ni(I)–Ni(III)–Ni(I) catalytic cycle.

酮是有机合成中最关键的组成部分之一，涉及许多官能团转化。在此，我们报告了一种前所未有的光氧化还原 - 镍金属光氧化还原催化的常见脂肪酸与容易获得的芳香族和脂肪族硫酯的脱羧酰化。使用这种策略已经构建了多种结构多样的不对称芳基烷基和二烷基酮，产率高达 98%。该方案具有出色的反应选择性和官能团兼容性，代表了酮合成向前迈出的重要一步。两种不同羧酸的克级一锅脱羧酰化反应和合成复杂酮的后期应用显示了其合成稳定性。