Photocatalyzed Epimerization of Quaternary Stereocenters,Journal of the American Chemical Society

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Photocatalyzed Epimerization of Quaternary Stereocenters
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2025-03-19 , DOI: 10.1021/jacs.4c16769
Licheng Wu ₁ , Baylee N McIntyre ₁ , Supeng Wu ₁ , Ziqi Jiao ₁ , Carter B Fox ₁ , Nathan D Schley ₁ , Alexander W Schuppe ₁

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Quaternary stereocenters play a crucial role in shaping both the molecular topology of small molecules and the outcome of stereoselective transformations. While considerable progress has been achieved in constructing highly substituted carbon centers with varied substitution patterns, the stereoselective synthesis of quaternary carbon centers remains a significant challenge. Here we report a protocol for the precise manipulation of quaternary stereocenters through epimerization. The critical design element of our ketone α-epimerization process was developing a photoactive imine, which circumvents the numerous deleterious pathways of carbonyl photochemistry. Excitation of this imine with visible light in the presence of a photocatalyst enables reversible C–C bond cleavage and reformation to vary the stereochemistry of the quaternary center. This approach allows us to override intrinsic stereochemical outcomes of C–C bond construction, therefore providing novel tactics for retrosynthetic planning. The broad utility of this protocol was demonstrated by the topological alteration of various classes of carbocyclic scaffolds bearing diverse functional groups.

中文翻译：

四纪立体中心的光催化差向异构化

四元立体中心在塑造小分子的分子拓扑结构和立体选择性转换的结果中起着至关重要的作用。虽然在构建具有不同取代模式的高度取代碳中心方面取得了相当大的进展，但四元碳中心的立体选择性合成仍然是一个重大挑战。在这里，我们报告了一种通过差向异构化精确纵四元立体中心的方案。我们的酮 α-差向异构化过程的关键设计要素是开发一种光活性亚胺，它规避了羰基光化学的众多有害途径。在光催化剂存在下用可见光激发这种亚胺，使可逆的 C-C 键裂解和重整能够改变四元中心的立体化学。这种方法使我们能够覆盖 C-C 键构建的内在立体化学结果，从而为逆合成规划提供新的策略。该方案的广泛用途通过带有不同官能团的各种类别的碳环支架的拓扑改变得到证明。

更新日期：2025-03-19

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