近日，郑州大学邓瑞显团队研究了如何实现烯醇化物区域选择性：通过可切换的C-和O-酰化反应在催化剂引导下分散合成阻转异构吡啶酮类。相关论文发表在2025年7月14日出版的《美国化学会志》杂志上。

催化剂引导的发散合成标志着有机合成的范式转变，为获得结构多样的分子提供了变革的潜力。

通过利用对称烯醇化物作为可编程合成子，研究组建立了一种催化引导的可切换的C-和O酰化反应，用于N-C和N-N轴向手性吡啶酮的发散合成。对映体和区域控制（C-酰化vs O-酰化）的突出表现源于新型手性4-吡咯烷二吡啶（PPY）衍生物和PPY- N-氧化物作为正交酰基转移催化剂的开发。这些催化剂表现出互补反应性，并选择性地递送C或O酰化产物。值得注意的是，它们卓越的抗缩选择性控制能力使得C-N和N-N抗缩异构体的可及性成为可能，扩大了这类常规催化剂可及性手性结构的范围。后功能化进一步显示了该方法在获取结构复杂的手性框架方面的潜力。

附：英文原文

Title: Taming Enolate Regioselectivity: Catalyst-Guided Divergent Synthesis of Atropisomeric Pyridones via Switchable C- and O-Acylation

Author: Jun Qin, Jimeng Ge, Hongyu Qu, Xiaoping Xue, Zhenhua Gu, Ruixian Deng

Issue&Volume: July 14, 2025

Abstract: Catalyst-guided divergent synthesis marks a paradigm shift in organic synthesis, offering transformative potential to access structurally diverse molecules. By leveraging symmetric enolates as programmable synthons, we established a catalyst-guided atroposelective C- and O-acylation for the switchable divergent synthesis of N–C and N–N axially chiral pyridones. The outstanding enantio- and regiocontrol (C- vs O-acylation) originated from the development of new chiral 4-pyrrolidinopyridine (PPY) derivatives and PPY-N-oxides as orthogonal acyl-transfer catalysts. These catalysts exhibited complementary reactivity and selectively delivered C- or O-acylated products. Notably, their exceptional atroposelective control capabilities enabled access to both C–N and N–N atropisomers, expanding the scope of accessible chiral architectures of conventional catalysts in this class. The synthetic applications were further displayed by the postfunctionalization, underscoring the methodology’s potential in accessing structurally complex chiral frameworks.

DOI: 10.1021/jacs.5c07688

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.5c07688