From Esters to Ketones via a Photoredox-Assisted Reductive Acyl Cross-Coupling Strategy

Xiaoxiang Xi; Yixin Luo; Weirong Li; Minghao Xu; Hongping Zhao; Yukun Chen; Songlin Zheng; Xiaotian Qi; Weiming Yuan

doi:10.1002/anie.202114731

From Esters to Ketones via a Photoredox-Assisted Reductive Acyl Cross-Coupling Strategy

Angew Chem Int Ed Engl. 2022 Jan 17;61(3):e202114731. doi: 10.1002/anie.202114731. Epub 2021 Dec 2.

Authors

Xiaoxiang Xi¹, Yixin Luo², Weirong Li¹, Minghao Xu², Hongping Zhao¹, Yukun Chen¹, Songlin Zheng¹, Xiaotian Qi², Weiming Yuan¹

Affiliations

¹ Key Laboratory of Material Chemistry for Energy Conversion and Storage, Ministry of Education, Hubei Key Laboratory of Bioinorganic Chemistry and Materia Medica, School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology (HUST), 1037 Luoyu Road, Wuhan, 430074, P. R. China.
² Engineering Research Center of Organosilicon Compounds & Materials, Ministry of Education, College of Chemistry and Molecular Sciences, Wuhan University, Wuhan, Hubei, 430072, P. R. China.

PMID: 34783143
DOI: 10.1002/anie.202114731

Abstract

A method was developed for ketone synthesis via a photoredox-assisted reductive acyl cross-coupling (PARAC) using a nickel/photoredox dual-catalyzed cross-electrophile coupling of two different carboxylic acid esters. A variety of aryl, 1°, 2°, 3°-alkyl 2-pyridyl esters can act as acyl electrophiles while N-(acyloxy)phthalimides (NHPI esters) act as 1°, 2°, 3°-radical precursors. Our PARAC strategy provides an alternative and reliable way to synthesize various sterically congested 3°-3°, 3°-2°, and aryl-3° ketones under mild and highly unified conditions, which have been otherwise difficult to access. The combined experimental and computational studies identified a Ni⁰ /Ni^I /Ni^III pathway for ketone formation.

Keywords: ketones; nickel; photocatalysis; visible light.

Abstract

Grants and funding