Photoexcitation of Distinct Divalent Palladium Complexes in Cross-Coupling Amination Under Air.

The development of metal complexes that function as both photocatalyst and cross-coupling catalyst remains a challenging research topic. So far, progress has been shown in palladium(0) excited-state transition metal catalysis for the construction of carbon-carbon bonds where the oxidative addition of alkyl/aryl halides to zero-valent palladium (Pd0 ) is achievable at room temperature. In contrast, the analogous process with divalent palladium (PdII ) is uphill and endothermic. For the first time, we report that divalent palladium can act as a light-absorbing species that undergoes double excitation to realize carbon-nitrogen (C-N) cross-couplings under air. Differently substituted aryl halides can be applied in the mild, and selective cross-coupling amination using palladium acetate as both photocatalyst and cross-coupling catalyst at room temperature. Density functional theory studies supported by mechanistic investigations provide insight into the reaction mechanism.

Oxidative Addition to Palladium(0) Made Easy through Photoexcited-State Metal Catalysis: Experiment and Computation.

Visible-light induced, palladium catalyzed alkylations of α,ß-unsaturated acids with unactivated alkyl bromides are described. A variety of primary, secondary, and tertiary alkyl bromides are activated by the photoexcited palladium metal catalyst to provide a series of olefins at room temperature under mild reaction conditions. Mechanistic investigations and density functional theory (DFT) studies suggest that a photoinduced inner-sphere mechanism is operative in which a barrierless, single-electron transfer oxidative addition of the alkyl halide to Pd0 is key for the efficient transformation.

Dehydrogenative Aromatization and Sulfonylation of Pyrrolidines: Orthogonal Reactivity in Photoredox Catalysis.

Oxidative dehydrogenative aromatization and selective sulfonylation reactions of N-heterocycles under visible-light photoredox catalysis were established. The mild reaction conditions make this approach an appealing and versatile strategy to functionalize/oxidize pyrrolidines whereby arylsulfonyl chlorides were identified to be both catalyst regeneration and sulfonylation reagents.

Cobalt-Catalyzed Oxidative Annulation of Nitrogen-Containing Arenes with Alkynes: An Atom-Economical Route to Heterocyclic Quaternary Ammonium Salts.

Four cobalt-catalyzed oxidative annulation reactions of nitrogen-containing arenes with alkynes proceeds by C-H activation, thus leading to biologically useful quaternary ammonium salts, including pyridoisoquinolinium, cinnolinium, isoquinolinium, and quinolizinium salts, in high yields. The results are comparable to those reactions catalyzed by rhodium and ruthenium complexes. The transformation of the salts into various N-heterocycles has also been demonstrated.

Excited-State Nickel-Catalyzed Amination of Aryl Bromides: Synthesis of Diphenylamines and Primary Anilines.

Excited-state nickel-catalyzed C-N cross-coupling of aryl bromides with sodium azide enables the synthesis of diarylamines and primary anilines under mild reaction conditions. The oxidative addition of electron-rich aryl bromides with low-valent Ni under the photochemical conditions is endothermic. Herein, we demonstrate a light-mediated nickel-catalyzed reaction of electronically rich aryl bromides that yields diarylamines, while the reaction with electron-deficient aryl bromides gives access to anilines at room temperature.

Rhodium(III)-catalyzed synthesis of cinnolinium salts from azobenzenes and alkynes: application to the synthesis of indoles and cinnolines.

Versatile salts: A new rhodium-catalyzed synthesis of cinnolinium salts from various azobenzenes and alkynes under air is described. These salts readily transform into three important classes of products, including indoles, indoloindoles, and cinnolines (see scheme).

Mechanistic insights into excited-state palladium catalysis for C-S bond formations and dehydrogenative sulfonylation of amines.

Photocatalytic selective C(sp3)-H activation/cross-coupling reactions are appealing in organic synthesis. In this manuscript, we describe the development of photoexcited-state Pd-catalyzed dehydrogenative ß-sulfonylation reactions using amines and aryl sulfonyl chlorides via intermolecular hydrogen atom transfer and C-S cross-coupling processes at room temperature. The transformation can be achieved by the direct generation of two distinct Pd-radical hybrid species and their capability to promote two different reactivities from Pd(0) and aryl sulfonyl chlorides, allowing for the efficient conversion of readily available amines into stable sulfonyl-substituted enamines at room temperature. The in-depth experimental, computational, and transient optical spectroscopic study and catalytic applications of a dehydrogenative functionalization event provide evidence for both static and dynamic quenching, as well as inner-sphere and outer-sphere mechanisms.

Excited-state palladium-catalysed reductive alkylation of imines: scope and mechanism.

Palladium catalysis induced by visible-light irradiation is a promising tool for promoting unusual chemical transformations. We describe the development of excited-state palladium-catalyzed reductive alkylation of imines with alkyl bromides. The new methodology shows broad functional group tolerance and can additionally be applied in the direct three-component reaction of aldehydes, anilines, and alkyl bromides to give the alkyl amines under mild reaction conditions. Time-resolved photoluminescence experiments allowed the determination of the excited-state reaction kinetics and indicate that the reaction is proceeding via the inner-sphere electron transfer mechanism.

Paired Electrolysis for Decarboxylative Cyanation: 4-CN-Pyridine, a Versatile Nitrile Source.

A decarboxylative cyanation of amino acids under paired electrochemical reaction conditions has been developed. 4-CN-pyridine was found to be a new and effective cyanation reagent under catalyst-free conditions. Mechanistic studies support a nucleophilic reaction pathway, and the cyanation protocol can be applied to diverse substrates including N,N-dialkyl aniline and indole derivatives.

Mechanistic insights into photochemical nickel-catalyzed cross-couplings enabled by energy transfer.

Various methods that use a photocatalyst for electron transfer between an organic substrate and a transition metal catalyst have been established. While triplet sensitization of organic substrates via energy transfer from photocatalysts has been demonstrated, the sensitization of transition metal catalysts is still in its infancy. Here, we describe the selective alkylation of C(sp3)-H bonds via triplet sensitization of nickel catalytic intermediates with a thorough elucidation of its reaction mechanism. Exergonic Dexter energy transfer from an iridium photosensitizer promotes the nickel catalyst to the triplet state, thus enabling C-H functionalization via the release of bromine radical. Computational studies and transient absorption experiments support that the reaction proceeds via the formation of triplet states of the organometallic nickel catalyst by energy transfer.

Unactivated Alkyl Chloride Reactivity in Excited-State Palladium Catalysis.

Excited-state palladium catalysis is an efficient process for the alkylation of diverse organic compounds via the generation of alkyl radicals from alkyl bromides and iodides. However, the generation of alkyl radicals from more stable alkyl chlorides remains challenging. Herein, we demonstrate the excited-state palladium-catalyzed synthesis of oxindoles and isoquinolinediones via alkylation/annulation reaction by overcoming inherent limitations associated with unactivated C(sp3)-Cl bond activation at room temperature.

A simple route to 1,4-addition reactions by Co-catalyzed reductive coupling of organic tosylates and triflates with activated alkenes.

An efficient Co-catalyzed 1,4-addition reaction of alkyl/aryl triflates and tosylates with activated alkenes is described. In this reaction, an air-stable cobalt(ii) complex, a mild reducing agent Zn and a simple proton source (H2O) are used. A radical mechanism for the addition of alkyl tosylates to activated alkenes is likely involved.

Rh-catalyzed oxidizing group-directed ortho C-H vinylation of arenes by vinylstannanes.

An efficient method for the synthesis of functionalized vinyl arenes from the reaction of N-methoxybenzamides or N-phenoxyacetamides with vinylstannanes via rhodium(iii)-catalyzed C-H activation is described. The application of the methodology for the synthesis of a natural product thalactamine and a 7-membered ring oxepine are also demonstrated.

Ru(II)-catalyzed amidation of 2-arylpyridines with isocyanates via C-H activation.

An efficient Ru(II)-catalyzed amidation of 2-arylpyridines with isocyanates via C-H bond activation is described.