Direct enantioselective reduction of C=C bond of β-polyfluoro-alkylated enones via asymmetric photoredox catalysis

• Published in: Science China. Chemistry Vol. 67; no. 6; pp. 2016 - 2021
• Main Authors: Zhang, Linghong, Ma, Jin, Ban, Xu, Zhao, Xiaowei, Yin, Yanli, Jiang, Zhiyong
• Format: Journal Article
• Language: English
• Published: Beijing Science China Press 01.06.2024; Springer Nature B.V
• Subjects: Alkylation; Asymmetry; Catalysis; Chemistry; Chemistry and Materials Science; Chemistry/Food Science; Deuteration; Deuterium; Enantiomers; Hydrogen bonding; Hydrogenation; NMR; Nuclear magnetic resonance; Photoredox catalysis; Single electrons; Success; photoredox catalysis; asymmetric reduction; enantioselective protonation; Brønsted acids; azaarenes
• ISSN: 1674-7291; 1869-1870
• DOI: 10.1007/s11426-023-1896-5

Direct enantioselective reduction of the C=C bond of β-polyfluoro-alkylated enones is an important but long-pending subject in asymmetric catalysis. Here, we report on the viability of visible light-driven cooperative photoredox and chiral hydrogen-bonding catalysis to effectively address this challenge, as a variety of products are obtained in high yields (up to 85%) with good to excellent enantioselectivities (up to 98% ee). The formation of thermodynamically favorable enol intermediates after double single-electron reduction represents the center of the success. Additionally, the utility of the current method is validated by the convenient regio-specific and -diverse synthesis of various deuterated derivatives for these products using inexpensive D 2 O as the deuterium source.