通过光氧化还原/铜双催化合成α-氟化芳基乙酸酯。
Synthesis of α-Fluorinated Areneacetates through Photoredox/Copper Dual Catalysis.
机构信息
Roy and Diana Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104-6323, United States.
出版信息
Org Lett. 2022 May 6;24(17):3194-3198. doi: 10.1021/acs.orglett.2c00969. Epub 2022 Apr 25.
Abstract
The development of mild and practical conditions for the fluoroalkylation of arenes is an ongoing challenge in chemical organic synthesis. Herein, we report a metallaphotoredox method for the preparation of fluoroalkyl arenes based on the synergistic combination of Ir/Cu dual catalysis from boronic acids. The mild conditions allow broad functional group tolerance, including substrates containing aldehydes, free phenols, and -Boc-protected amines. Mechanistic investigations support a process proceeding via photoredox/copper dual catalysis.
摘要
发展温和且实用的芳基氟烷基化条件是化学有机合成中一个持续的挑战。在此，我们报告了一种基于硼酸的 Ir/Cu 双催化协同组合的制备氟代芳基芳烃的金属光氧化还原方法。温和的条件允许广泛的官能团容忍性，包括含有醛、游离酚和-Boc 保护胺的底物。机理研究支持通过光氧化还原/铜双催化进行的过程。
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2
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3
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