After optimization for retention of catalytic activity, 4‐chlorobenzoic acid emerged as the optimal catalyst for the aliphatic ketone Claisen rearrangement. The optimal catalyst enables a one‐pot, metal‐free, catalytic protocol from allylic alcohols to γ,δ‐unsaturated ketones. The optimized process tolerates a range of substrates, including substituents with acid‐labile protecting groups. Reaction monitoring and DFT studies of the aliphatic ketone Claisen process agree that the ultimate rearrangement step typically has the highest activation barrier.

中文翻译：

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脂肪酮克莱森重排：通过识别稳定的酸催化剂排除醚交换步骤的故障


经过对催化活性保留的优化后，4-氯苯甲酸成为脂肪酮克莱森重排的最佳催化剂。最佳催化剂可实现从烯丙醇到 γ,δ-不饱和酮的一锅式、无金属催化方案。优化的工艺可耐受一系列底物，包括具有酸不稳定保护基团的取代基。脂肪酮克莱森过程的反应监测和 DFT 研究一致认为，最终重排步骤通常具有最高的活化势垒。