Visible light-driven deracemization of α-aryl ketones synergistically catalyzed by thiophenols and chiral phosphoric acid
Peer-Reviewed Publication
Updates every hour. Last Updated: 9-May-2026 07:15 ET (9-May-2026 11:15 GMT/UTC)
A collaborative research team comprised of Xin Li from Nankai University, Wei Zhang from Sichuan University, and Hanliang Zheng from Zhejiang Normal University developed a green and efficient photo-redox/hydrogen atom transfer (HAT)/chiral phosphoric acid (CPA) synergistic catalytic strategy to achieve the deracemization of α-aryl cyclic ketones, successfully synthesizing a series of chiral α-aryl cyclic ketones (Figure 1). The reaction generates a sulfur radical via a proton-coupled electron transfer (PCET) process between an excited-state photosensitizer and a thiophenol, followed by hydrogen atom transfer and single-electron reduction to form a key enol intermediate. Finally, an asymmetric keto-enol tautomerism occurs under chiral phosphoric acid catalysis, achieving deracemization. A series of mechanistic experiments and density functional theory (DFT) calculations support the above reaction pathway and further reveal that conformational distortion of the chiral catalyst in the unfavorable transition state is a key factor in regulating the enantioselectivity of the reaction. The article was published as an open access Research Article in CCS Chemistry, the flagship journal of the Chinese Chemical Society.
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