Heteroleptic copper(I) complexes [Cu(dmp)(N^P)]BF for photoinduced atom-transfer radical addition reactions.

Earth-abundant copper(I) coordination complexes of an imine-phosphine and a diimine have been developed as visible-light photocatalysts. Reaction of [Cu(MeCN)]BF with hetero-bidentate phosphinopyrazole (phpz) ligand RRCHNPPh (R = R = H (1a); R = H, R = Me (1b); R = H, R = Ph (1c); R = R = Me (1d)) and 2,9-dimethyl-1,10-phenanthroline (dmp) gave four heteroleptic bis-chelate Cu(I) complexes [Cu(dmp)(RRCHNPPh)]BF (R = R = H (2a); R = H, R = Me (2b); R = H, R = Ph (2c); R = R = Me (2d)) with distorted tetrahedral geometries. Complexes 2a-2d exhibited broad absorption in the visible spectrum and could facilitate photochemical intermolecular atom-transfer radical addition reactions of CBr, or CClBr, CHI to styrenes in yields up to 91% and with a broad substrate scope.

Visible-light-driven C(sp)-H arylation of phenols with arylbromides enabled by electron donor-acceptor excitation.

We have developed a catalyst-free visible-light-driven C(sp)-H arylation of unprotected phenols with arylbromides to give 2-arylated phenols. This reaction proceeds through the excitation of an electron donor-acceptor complex between a phenolate and an arylbromide, electron transfer, and debrominative C(sp)-C(sp) coupling.

Nickel-Catalyzed Etherification of Phenols and Aryl Halides through Visible-Light-Induced Energy Transfer.

Notwithstanding some progress in nickel-catalyzed etherification of alkanols and arylhalides, the ability of such a Ni-catalyzed transformation employing phenols to diaryl ethers is unsuccessful due to phenolates with much lower reduction potentials, which suppress the oxidation of nickel(II) intermediates into requisite Ni(III) species. We herein report visible-light-initiated, nickel-catalyzed O-arylation of phenols with arylhalides using -BuNH(-Pr) as the base and thioxanthen-9-one as the photosensitizer under visible light. This photocoupling exhibits a broad substrate scope.

Visible-Light-Induced Nickel-Catalyzed P(O)-C(sp) Coupling Using Thioxanthen-9-one as a Photoredox Catalysis.

An efficient method has been developed for photocatalytic P(O)-C(sp) coupling of (hetero)aryl halides with H-phosphine oxides or H-phosphites under the irradiation of visible light or sunlight. The thioxanthen-9-one/nickel dual catalysis mediates this phosphonylation to give arylphosphine oxides and arylphosphonates in moderate to excellent yields. This transformation is widely tolerant to a range of functional groups and proceeds efficiently on a gram scale.

Acyl Radicals from α-Keto Acids Using a Carbonyl Photocatalyst: Photoredox-Catalyzed Synthesis of Ketones.

Acyl radicals have been generated from α-keto acids using inexpensive and commercially available 2-chloro-thioxanthen-9-one as the photoredox catalyst under visible light illumination. These reactive species added to olefins or coupled with aryl halides via a bipyridyl-stabilized Ni(II) catalyst, enabling easy access to a diverse range of ketones. This reliable, atom-economical, and eco-friendly protocol is compatible with a wide range of functional groups.

Nickel-Catalyzed Sonogashira C(sp)-C(sp) Coupling through Visible-Light Sensitization.

An efficient method for visible-light-initiated, nickel-catalyzed Sonogashira C(sp)-C(sp) coupling has been developed via an energy-transfer mode. Thioxanthen-9-one as a photosensitizer could significantly accelerate the arylation of alkynes with a wide range of (hetero)aryl halides in high yields. The cross-coupling reaction undergoes the stepwise oxidative addition of an arylhalide to nickel(0), transmetalation of the resulting aryl-Ni(II) halide species with Zn(II) acetylide into aryl-Ni(II) acetylide species, energy transfer from the excited state of thioxanthen-9-one to aryl-Ni(II) acetylide, and reductive elimination to the aryl alkyne.

Hantzsch Ester as a Visible-Light Photoredox Catalyst for Transition-Metal-Free Coupling of Arylhalides and Arylsulfinates.

Diethyl 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate (HEH) has been utilized as a visible-light photoredox catalyst for the cross coupling of arylhalides and arylsulfinates without transition metal, sacrificial agent, and mediator. This method is compatible with various functional groups and provides diaryl sulfones in good to high yields. Mechanistic studies indicate that this reaction undergoes the stepwise light irradiation of HE , single electron transfer (SET) in donor-acceptor complex (DAC) from *HE to arylhalide, trapping of aryl radical with sulfinate, and SET oxidation of sulfone radical anion by HE to sulfone by the DAC method.

Exogenous Photosensitizer-, Metal-, and Base-Free Visible-Light-Promoted C-H Thiolation via Reverse Hydrogen Atom Transfer.

Visible-light-driven, intramolecular C(sp)-H thiolation has been achieved without addition of a photosensitizer, metal catalyst, or base. This reaction induces the cyclization of thiobenzanilides to benzothiazoles. The substrate absorbs visible light, and its excited state undergoes a reverse hydrogen-atom transfer (RHAT) with 2,2,6,6-tetramethylpiperidine N-oxyl to form a sulfur radical.

Preparation of carbon-based AuAg alloy nanoparticles by using the heterometallic [AuAg] cluster for efficient oxidative coupling of anilines.

We herein report the preparation of unique heteroatom-doped and carbon-based AuAg alloy nanoparticles (NPs) via the pyrolysis of a structurally defined octanuclear heterometallic Au(i)-Ag(i) cluster [Au4Ag4(Dppy)4(Tab)4(MeCN)4](PF6)8 (2, Dppy = diphenylphosphine-2-pyridine and Tab = 4-(trimethylammonio)benzenethiolate). This cluster-precursor approach exerts a fine control over the spatial arrangement, size and uniformity of the AuAg alloy NPs as well as the doped heteroatoms (P, N, F and S). The optimized material prepared at 450 °C efficiently catalyzes the oxidative coupling of anilines to yield azobenzenes under mild conditions.

Ligand-Controlled Copper(I)-Catalyzed Cross-Coupling of Secondary and Primary Alcohols to α-Alkylated Ketones, Pyridines, and Quinolines.

One hexanuclear Cu(I) cluster of 4,6-dimethylpyrimidine-2-thiolate efficiently catalyzes the dehydrogenative cross-coupling of secondary and primary alcohols to α-alkylated ketones with high selectivity. This transformation proceeds through a one-pot sequence of dehydrogenation of alcohols, condensation of aldehydes and ketones, hydrogenation of the resulting α,β-unsaturated ketones, and dehydrogenation of the α-alkylated alcohols to generate α-alkylated ketones. This catalytic system also displays high activity for the annulation reaction of secondary alcohols with γ-amino- and 2-aminobenzyl alcohols to yield pyridines and quinolines, respectively.