金属光氧化还原催化实现对映选择性烷基酰基交叉偶联，这一成果由厦门大学化学化工学院霍浩华研究组经过不懈努力而取得。相关论文于2025年2月19日发表在《美国化学会杂志》上。

研究人员报道了一种新的金属光氧化还原平台，使羧酸衍生物与醛的高度对映选择性脱羧偶联。他们的策略是通过微调一种普通光催化剂和一种简单的手性双（恶唑啉）镍催化剂来独立控制自由基的生成和随后的对映选择性键的形成。这种氧化还原-中性方案不需要外源氧化剂或还原剂，并且在合成对映体富集的α-芳基和α-氨基酮时显示出广泛的底物范围和官能团兼容性。α-氨基酮产物可以很容易地转化为有价值的β-氨基醇，从而简化了获得这些重要基序的途径。

此外，课题组研究人员还展示了这种方法在更具挑战性的对映选择性C(sp3) -C （sp3）烷基-烷基RCC反应中的潜力。这种对映选择性烷基-酰基自由基交叉偶联的统一平台代表了不对称催化的重大进展，并强调了金属光氧化还原催化开发新机制解决长期存在的合成问题的潜力。

研究人员表示，自由基-自由基交叉偶联（RCC）为有机合成中的碳-碳键形成提供了一种很有前途的方法，特别是在创建复杂的三维分子方面。然而，在RCC反应中实现交叉选择性和对映体选择性仍然是一个重大的挑战。

附：英文原文

Title: Enantioselective Alkyl–Acyl Radical Cross-Coupling Enabled by Metallaphotoredox Catalysis

Author: Tao Li, Zhen Xu, Yongliang Huang, Weisai Zu, Haohua Huo

Issue&Volume: February 19, 2025

Abstract: Radical–radical cross-coupling (RCC) offers a promising approach for carbon–carbon bond formation in organic synthesis, particularly for creating complex, three-dimensional molecules. However, achieving both cross- and enantioselectivity in RCC reactions has remained a significant challenge. Here, we report a novel metallaphotoredox platform that enables highly enantioselective decarboxylative coupling of carboxylic acid derivatives with aldehydes. Our strategy leverages independent control over radical generation and subsequent enantioselective bond formation through fine-tuning of a common photocatalyst and a simple chiral bis(oxazoline) nickel catalyst. This redox-neutral protocol requires no exogenous oxidants or reductants and demonstrates broad substrate scope and functional group compatibility in the synthesis of enantioenriched α-aryl and α-amino ketones. The α-amino ketone products can be readily transformed into valuable β-amino alcohols, streamlining access to these important motifs. Furthermore, we showcase the potential of this approach for more challenging enantioselective C(sp3)–C(sp3) alkyl–alkyl RCC reactions. This unified platform for enantioselective alkyl–acyl radical cross-coupling represents a significant advance in asymmetric catalysis and underscores the potential for metallaphotoredox catalysis to exploit new mechanisms to solve long-standing synthetic problems.

DOI: 10.1021/jacs.4c15275

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.4c15275