Photocatalytic Umpolung Synthesis of Nucleophilic π-Allylcobalt Complexes for Allylation of Aldehydes
Caizhe Shi, Fusheng Li, Yuqing Chen, Shuangjie Lin, Er‐Jun Hao, Zhuowen Guo, Urwa Tul Wosqa, Dandan Zhang, Lei Shi
Abstract
The concept of "umpolung" reactivity of π-allylmetal complexes has been developed as a powerful method for the allylation of aldehydes. This paper describes the photocatalytic umpolung strategy for the synthesis of nucleophilic allylcobalt complexes through a single-electron-transfer (SET) process. This strategy enables the metallaphotoredox allylation of carbonyls with allyl acetate using organic N,N-diisopropylethylamine as the terminal reductant bypassing the use of a stoichiometric amount of metals. Ultraviolet–visible spectroscopy was used to monitor the redox changes of cobalt in the reaction.
Topics & Concepts
UmpolungChemistryNucleophileReactivity (psychology)PhotocatalysisCatalysisCobaltRedoxPhotochemistryStoichiometryPhotoredox catalysisOrganic chemistryCombinatorial chemistryMedicineAlternative medicinePathologyCatalytic C–H Functionalization MethodsRadical Photochemical ReactionsOxidative Organic Chemistry Reactions