Autocatalytic photoredox Chan-Lam coupling of free diaryl sulfoximines with arylboronic acids
Open Access
- 9 February 2021
- journal article
- research article
- Published by Springer Science and Business Media LLC in Nature Communications
- Vol. 12 (1), 1-11
- https://doi.org/10.1038/s41467-021-21156-w
Abstract
N-Arylation of NH-sulfoximines represents an appealing approach to access N-aryl sulfoximines, but has not been successfully applied to NH-diaryl sulfoximines. Herein, a copper-catalyzed photoredox dehydrogenative Chan-Lam coupling of free diaryl sulfoximines and arylboronic acids is described. This neutral and ligand-free coupling is initiated by ambient light-induced copper-catalyzed single-electron reduction of NH-sulfoximines. This electron transfer route circumvents the sacrificial oxidant employed in traditional Chan-Lam coupling reactions, increasing the environmental friendliness of this process. Instead, dihydrogen gas forms as a byproduct of this reaction. Mechanistic investigations also reveal a unique autocatalysis process. The C-N coupling products, N-arylated sulfoximines, serve as ligands along with NH-sulfoximine to bind to the copper species, generating the photocatalyst. DFT calculations reveal that both the NH-sulfoximine substrate and the N-aryl product can ligate the copper accounting for the observed autocatalysis. Two energetically viable stepwise pathways were located wherein the copper facilitates hydrogen atom abstraction from the NH-sulfoximine and the ethanol solvent to produce dihydrogen. The protocol described herein represents an appealing alternative strategy to the classic oxidative Chan-Lam reaction, allowing greater substrate generality as well as the elimination of byproduct formation from oxidants. N-Arylation of NH-diaryl sulfoximines faces synthetic challenges among reported methods. Here, the authors present a mild copper-catalyzed photoredox dehydrogenative Chan-Lam coupling of free diaryl sulfoximines and arylboronic acids via an auto-catalytic process.Funding Information
- Shenzhen Science and Technology Innovation Commission (JCYJ20180302180256215)
This publication has 53 references indexed in Scilit:
- A Versatile Approach to Ullmann C–N Couplings at Room Temperature: New Families of Nucleophiles and Electrophiles for Photoinduced, Copper-Catalyzed ProcessesJournal of the American Chemical Society, 2013
- Sulfoximines: A Neglected Opportunity in Medicinal ChemistryAngewandte Chemie, 2013
- BAY 1000394, a Novel Cyclin-Dependent Kinase Inhibitor, with Potent Antitumor Activity in Mono- and in Combination Treatment upon Oral ApplicationMolecular Cancer Therapeutics, 2012
- Kinetic and Spectroscopic Studies of Aerobic Copper(II)-Catalyzed Methoxylation of Arylboronic Esters and Insights into Aryl Transmetalation to Copper(II)Organometallics, 2012
- Discovery and Characterization of Sulfoxaflor, a Novel Insecticide Targeting Sap-Feeding PestsJournal of Agricultural and Food Chemistry, 2010
- A Versatile and Highly Reactive Polyfluorinated Hypervalent Iodine(III) CompoundAngewandte Chemie, 2010
- Copper phthalocyanine complex as electrocatalyst for hydrogen evolution reactionElectrochemistry Communications, 2009
- A novel electrochemical immunosensor based on hydrogen evolution inhibition by enzymatic copper deposition on platinum nanoparticle-modified electrodeBiosensors and Bioelectronics, 2008
- A new mixing of Hartree–Fock and local density-functional theoriesThe Journal of Chemical Physics, 1993
- Acidities of sulfoximines and related oxosulfonium cations. Cyclopropyl effects and structures of .alpha.-sulfonyl-type carbanionsThe Journal of Organic Chemistry, 1980