Ni/Photoredox-Catalyzed Enantioselective Acylation of α-Bromobenzoates with Aldehydes: A Formal Approach to Aldehyde-Aldehyde Cross-Coupling,Journal of the American Chemical Society

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Ni/Photoredox-Catalyzed Enantioselective Acylation of α-Bromobenzoates with Aldehydes: A Formal Approach to Aldehyde-Aldehyde Cross-Coupling
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2024-06-12 , DOI: 10.1021/jacs.4c03164
Chengyang Li ₁ , Junliang Cheng ₁ , Xiang Wan ₁ , Jian Li ₁ , Weisai Zu ₁ , Yumin Xu ₁ , Yongliang Huang ₁ , Haohua Huo ₁

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The catalytic cross-coupling of identical or similar functional groups is a cornerstone strategy for carbon–carbon bond formation, as exemplified by renowned methods, such as olefin cross-metathesis, Kolbe electrolysis, and various cross-electrophile couplings. However, similar methodologies for coupling aldehydes─fundamental building blocks in organic synthesis─remain underdeveloped. While the benzoin-type condensation, first reported in 1832, offers a reliable route for aldehyde dimerization, the chemo- and enantioselective cross-coupling of nonidentical yet similar aldehydes remains an unsolved challenge. Herein, we report a unified platform enabling highly chemo- and enantioselective cross-coupling of aldehydes. By leveraging nickel photoredox catalysis in tandem with discrete activation strategies for each aldehyde, this mechanistically distinct approach facilitates the enantioselective union of an aldehyde-derived α-oxy radical with an acyl radical, photocatalytically generated from a distinct aldehyde. This novel strategy enables modular access to enantioenriched α-oxygenated ketones with two minimally differentiated aliphatic substituents, a feat not achievable with existing chemocatalytic or biocatalytic techniques. The synthetic utility of this method is demonstrated by its application in the streamlined asymmetric synthesis of various medicinally relevant molecules. Additionally, mechanistic investigations rationalize the versatility of nickel photoredox catalysis to exploit new pathways for addressing long-standing synthetic challenges.

中文翻译：

Ni/光氧化还原催化 α-溴苯甲酸酯与醛的对映选择性酰化：醛-醛交叉偶联的正式方法

相同或相似官能团的催化交叉偶联是碳-碳键形成的基石策略，例如烯烃交叉复分解、科尔贝电解和各种交叉亲电子偶联等著名方法。然而，用于偶联醛（有机合成的基本组成部分）的类似方法仍未得到开发。虽然 1832 年首次报道的安息香型缩合为醛二聚提供了可靠的途径，但不同但相似的醛的化学和对映选择性交叉偶联仍然是一个尚未解决的挑战。在此，我们报告了一个统一的平台，可实现醛的高度化学和对映选择性交叉偶联。通过利用镍光氧化还原催化与每种醛的离散活化策略，这种机械上不同的方法促进了醛衍生的 α-氧基自由基与酰基自由基的对映选择性结合，酰基自由基是由不同的醛光催化产生的。这种新颖的策略使得能够模块化地获得具有两个最小差异脂肪族取代基的对映体富集的α-氧化酮，这是现有化学催化或生物催化技术无法实现的壮举。该方法的合成效用通过其在各种医学相关分子的简化不对称合成中的应用得到证明。此外，机理研究合理化了镍光氧化还原催化的多功能性，以探索解决长期存在的合成挑战的新途径。

更新日期：2024-06-12

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