Herein, we report a mild, operationally simple, multicatalytic method for the synthesis of β,γ-unsaturated ketones via allylic acylation of alkenes. Specifically, the method combines N‑heterocyclic carbene catalysis, hydrogen atom transfer catalysis, and photoredox catalysis for cross-coupling reactions between a wide range of feedstock carboxylic acids and readily available olefins to afford structurally diverse β,γ-unsaturated ketones without olefin transposition. The method could be used to install acyl groups on highly functionalized natural-product-derived compounds with no need for substrate pre-activation, and C–H functionalization proceed with excellent site selectivity. To demonstrate the potential applications of the method, we convert a representative coupling product into various useful olefin synthons.

在此，我们报告了一种温和、操作简单的多催化方法，用于通过烯烃的烯丙基酰化合成β,γ-不饱和酮。具体而言，该方法结合了N-杂环卡宾催化、氢原子转移催化和光氧化还原催化，用于各种原料羧酸和现成烯烃之间的交叉偶联反应，以提供结构多样的 β, γ-没有烯烃转位的不饱和酮。该方法可用于在高度功能化的天然产物衍生化合物上安装酰基，无需底物预活化，并且 C-H 功能化过程具有出色的位点选择性。为了展示该方法的潜在应用，我们将具有代表性的偶联产物转化为各种有用的烯烃合成子。