title: Visible-Light-Promoted Nickel- and Organic-Dye-Cocatalyzed Formylation Reaction of Aryl Halides and Triflates and Vinyl Bromides with Diethoxyacetic Acid as a Formyl Equivalent.
abstract: A simple formylation reaction of aryl halides, aryl triflates, and vinyl bromides under synergistic nickel- and organic-dye-mediated photoredox catalysis is reported. Distinct from widely used palladium-catalyzed formylation processes, this reaction proceeds by a two-step mechanistic sequence involving initial in situ generation of the diethoxymethyl radical from diethoxyacetic acid by a 4CzIPN-mediated photoredox reaction. The formyl-radical equivalent then undergoes nickel-catalyzed substitution reactions with aryl halides and triflates and vinyl bromides to form the corresponding aldehyde products. Significantly, besides aryl bromides, less reactive aryl chlorides and triflates and vinyl halides serve as effective substrates for this process. Since the mild conditions involved in this reaction tolerate a plethora of functional groups, the process can be applied to the efficient preparation of diverse aromatic aldehydes.
authors.affiliation: Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, NM, 87131, USA.
authors.forename: He
authors.initials: H
authors.lastname: Huang
authors.affiliation: Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, NM, 87131, USA.|State Key Laboratory of Bioengineering Reactor and Shanghai Key Laboratory of New Drug Design, School of Pharmacy, East China University of Science & Technology, 130 Mei-Long Road, Shanghai, 200237, P.R. China.
authors.forename: Xiangmin
authors.initials: X
authors.lastname: Li
authors.affiliation: Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, NM, 87131, USA.
authors.forename: Chenguang
authors.initials: C
authors.lastname: Yu
authors.affiliation: Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, NM, 87131, USA.
authors.forename: Yueteng
authors.initials: Y
authors.lastname: Zhang
authors.affiliation: Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, NM, 87131, USA.
authors.forename: Patrick S
authors.initials: PS
authors.lastname: Mariano
authors.affiliation: Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, NM, 87131, USA.|State Key Laboratory of Bioengineering Reactor and Shanghai Key Laboratory of New Drug Design, School of Pharmacy, East China University of Science & Technology, 130 Mei-Long Road, Shanghai, 200237, P.R. China.
authors.forename: Wei
authors.identifier: 0000-0001-6043-0860
authors.initials: W
authors.lastname: Wang
keywords: flow chemistry; formylation; nickel catalysis; photoredox catalysis; synthetic methods