A highly effective hydroxylation reaction of aryl halides with water under synergistic organophotoredox and nickel catalysis is reported. The OH group of the resulting phenols originates from water, following deprotonation facilitated by an intramolecular base group on the ligand. Significantly, aryl bromides as well as less reactive aryl chlorides served as effective substrates to afford phenols with a wide range of functional groups. Without the need for a strong inorganic base or an expensive noble-metal catalyst, this process can be applied to the efficient preparation of diverse phenols and enables the hydroxylation of multifunctional pharmaceutically relevant aryl halides.
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http://dx.doi.org/10.1002/anie.201710698 | DOI Listing |
J Org Chem
January 2025
Department of Chemistry, University of Wisconsin-Madison, Madison, Wisconsin 53706, United States.
Org Lett
January 2025
School of Chemistry and Chemical Engineering, Nanchang University, Nanchang, Jiangxi 330031, P. R. China.
A Ni/photoredox dual-catalyzed multicomponent cross-electrophile coupling of N-vinyl amides with (hetero)aryl halides and (2°, 3°)-alkyl redox-active esters in the presence of cheap reductant Hantzsch ester is reported here. This reductive protocol provides direct access to various synthetically challenging chiral α-arylamides in good yields and excellent enantioselectivities (up to 99% ee, with the majority exceeding 97% ee), which can be further derived into chiral primary and secondary amines. Preliminary experimental studies shed light on the potential catalytic pathways.
View Article and Find Full Text PDFChemistryOpen
January 2025
University Paris Est Creteil, CNRS, ICMPE, UMR 7182, 2 rue Henri Dunant, 94320, Thiais, France.
The direct electrochemical carboxylation of aryl, benzyl and alkyl halides by CO is described using a magnesium anode and a nickel foam cathode in an undivided cell. The process employs a sacrificial anode and does not require the additional use of a transition metal catalyst or demanding conditions, as the reactions are carried out under galvanostatic mode, at -10 °C and with commercial DMF. Under these operationally simple conditions, an important range of carboxylic acids are affordable.
View Article and Find Full Text PDFNat Commun
January 2025
State Key Laboratory of Organometallic Chemistry, Shanghai of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, Shanghai, PR China.
Motivated by the inherent benefits of synergistically combining electrochemical methodologies with nickel catalysis, we present here a Ni-catalyzed enantioselective electroreductive cross-coupling of benzyl chlorides with aryl halides, yielding chiral 1,1-diaryl compounds with good to excellent enantioselectivity. This catalytic reaction can not only be applied to aryl chlorides/bromides, which are challenging to access by other means, but also to benzyl chlorides containing silicon groups. Additionally, the absence of a sacrificial anode lays a foundation for scalability.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Department of Chemistry, School of Science, Tianjin University, Tianjin 300072, China.
Electrocatalytic dehalogenative deuteration is a sustainable method for precise deuteration, whereas its Faradaic efficiency (FE) is limited by a high overpotential and severe D evolution reaction (DER). Here, Cu site-adjusted adsorption and crown ether-reconfigured interfacial DO are reported to cooperatively increase the FE of dehalogenative deuteration up to 84% at -100 mA cm. Cu sites strengthen the adsorption of aryl iodides, promoting interfacial mass transfer and thus accelerating the kinetics toward dehalogenative deuteration.
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