Abstract An unprecedented visible‐light‐induced direct C−H bond difluoroalkylation of aldehyde‐derived hydrazones was developed. This reaction represents a new way to synthesize substituted hydrazones. The salient features this include difluorinated hydrazone synthesis rather than classical amine synthesis, extremely mild conditions, high efficiency, wide substrate scope, ease in further transformations the products, and one‐pot syntheses. Mechanistic analyses theoretical calculations...

ConspectusThe chemistry of hydrazones has gained great momentum due to their involvement throughout the evolution organic synthesis. Herein, we discuss tremendous developments in both methodology and application hydrazones. Hydrazones can be recognized not only as synthetic equivalents aldehydes ketones but also versatile building blocks. Consequently, they participate a range practical transformations. Furthermore, hydrazone derivatives display broad array biological activities have been...

An operationally simple and highly selective Au/Ag bimetallic-catalyzed cross-dehydrogenative biaryl coupling between pyrazoles fluoroarenes has been developed. With this reaction, a wide range of biheteroaryl products can be obtained in moderate to good yields with excellent functional group compatibility. The exact role silver salts, previously overlooked most gold-catalyzed transformations, carefully investigated coupling. Insightful experimental theoretical studies indicate that acetate...

The novel cascade photoredox/iodide catalytic system enables the alkene to serve as a radical acceptor capable of achieving aminodifluoroalkylation alkenes. Cheap iodide salts play vital role in this reaction, which could tune carbocation reactivity through reversible C–I bond formation for controlling reaction selectivity, and series competitive reactions are completely eliminated presence multiple pathways. present dual protocol affords very convenient method direct synthesis various...

The amidated peptides are an important class of biologically active compounds due to their unique biological properties and wide applications as potential peptide drugs biomarkers. Despite the abundance free amide motifs (Asn, Gln, C-terminal amide) in native peptides, late-stage modification unit naturally occurring remains very rare because intrinsically weak nucleophilicity amides interference multiple competing nucleophilic residues, which generally lead undesired side reactions. Herein,...

The enormous and widespread use of organoboronic acids has prompted the development innovative synthetic methodologies to meet demands on structural diversity functional group tolerance. existing photoinduced defunctionalization radical borylation, typically focused conversion one C-X bond (X= Br, I, or other leaving group) into only C-B bond. Herein, we disclose a divergent dechloroborylation reaction enabled by dinuclear gold catalysis with visible light irradiation. A wide range...

A hydroacylation reaction of alkenes has been achieved employing readily available carboxylic acids as the acyl source and hydrosilanes a hydrogen via photoredox catalysis. The combination both single electron transfer atom steps dramatically expanded new applications in organic synthesis. protocol also features extremely mild conditions, broad substrate scope, good functional group tolerance, affording novel convenient approach to alkenes.

A visible light mediated radical–radical coupling reaction towards the construction of valuable nitrogen heterocycles has been developed. Piperidine, pyrrolidine, indole, and azetidine scaffolds were synthesized in good to excellent yields from simple substrates.

In this paper, we report a mild and practical method for precise deuteration of aliphatic carboxylic acids by synergistic photoredox HAT catalysis. The reaction delivers excellent D-incorporation (up to 99%) at predicted sites even in substrates bearing reactive C-H bonds or versatile functional groups. use recirculation reactor with peristaltic pump supports scalable preparative ability 50 mmol) under very conditions. readily available complex makes protocol promising the preparation...

Selective deuteration of unactivated C(sp3)-H bonds is a highly attractive but challenging subject research in pharmaceutical chemistry, material science and synthetic chemistry. Reported herein practical, selective economical efficient hydrogen/deuterium (H/D) exchange by synergistic photocatalysis hydrogen atom transfer (HAT) catalysis. With the easily prepared PMP-substituted amides as nitrogen-centered radical precursors, wide range structurally diverse can undergo predictable H/D...

Exploration of elementary reactions in organometallic catalysis is an important method with which to discover new reactions. In this article, we report a gold(I)-catalyzed iodo-alkynylation benzyne involving the merging challenging migratory insertion and oxidative addition process gold catalytic cycle. A wide range structurally diverse alkynyl iodides are good coupling partners transformation. Both aliphatic aromatic can react benzynes smoothly afford highly functionalized 1,2-disubstituted...

Controlling the cross-coupling reaction between two different radicals is a long-standing challenge due to process occurring statistically, which would lead three products, including homocoupling products and one product. Generally, selectivity achieved by persistent radical effect (PRE) that requires presence of transient radical, thus resulting in limited precursors. In this paper, highly selective alkyl with acyl construct C(sp

A visible light promoted C(sp3)–H difluoromethylation of tetrahydroisoquinolines that uses stable and easily prepared α,α-difluorinated gem-diol as the CF₂ source is disclosed.

A copper-catalyzed tandem radical cyclization of 1-(3-phenylprop-2-yn-1-yl)-1H-indole with diphenylphosphine oxides was developed. C–P bond formation achieved coupled C(sp2)–H functionalization. It provided an access to construct the pyrrolo[1,2-a]indole motif and a series 2-phosphinoyl-9H-pyrrolo[1,2-a]indoles.

A straightforward and efficient protocol for the construction of structurally biologically interesting chiral flavanoids incorporating three privileged structures, i.e., chromanone, dihydropyran, indole, has been developed on basis bifunctional tertiary amine thiourea-catalyzed asymmetric inverse-electron-demand Diels-Alder reaction chromone heterodienes 3-vinylindoles, which were used as dienophiles.

Domino-fluorination–protodefluorination decarboxylative cross-coupling of α-keto acids with styrene has been developed via photoredox catalysis. The critical part this strategy is the formation carbon–fluorine (C–F) bond by capture a carbon-centered radical intermediate, which will overcome side reactions during functionalization process. Experimental studies have provided evidence indicating domino-fluorination–protodefluorination pathway acid initiating cycle. present catalytic protocol...

A relay visible-light photoredox catalysis strategy has been accomplished. Three successive cycles (one oxidative quenching cycle and two reductive cycles) are engaged in a single reaction with one photocatalyst. This enables formal [4 + 1] annulation of hydrazones 2-bromo-1,3-dicarbonyl compounds, which functionalizes three C–H bonds hydrazones. method affords rapid access to complex biologically important pyrazole scaffold step-economical manner high efficiency under mild conditions.

A silver-catalyzed cascade cyclization of cinnamamides with diphenylphosphine oxide was developed, in which activation the P-H bond and functionalization C(sp(2))-H occurred. direct method for synthesis 3,4-disubstituted dihydroquinolin-2(1H)-ones developed.

A highly efficient catalytic dearomatization of indoles <italic>via</italic> visible-light photocatalysis is presented. The common indole tethered alcohol at the N1 or C2 position reacts in a cascade fashion, providing facile access to diverse indolone scaffolds.

Visible-light-mediated tandem radical difluoroalkylation and alkynylation of unactivated alkenes is described. It comprises a mild C–C bond activation <italic>via</italic> intramolecular 1,4-radical alkynyl migration.

A novel visible light photoredox catalysis three-component 1,2-difluoroalkylarylation of styrenes was disclosed, and two new C–C bonds were generated in a single step through regioselective incorporation CF₂ group variety indoles to CC bonds.

We have developed a general and site-predictable manganese-catalyzed hydroarylation of internal alkynes in the presence water, under an air atmosphere without involvement ligand. The unique catalytic feature this reaction is highlighted by comparison with other widely used transition metal catalysts including palladium, rhodium, nickel, or copper. simple operation, high efficiency excellent functional group compatibility make protocol practical for more than 90 structurally diverse alkynes,...

Comprehensive Summary In this paper, we have developed a decarboxylative amination of carboxylic acids with nitroarenes for the synthesis secondary amines. The protocol is performed at mild conditions without use noble metals as catalysts. A wide range structurally diverse amines could be obtained in good yields (up to 94%) functional group tolerance. This transformation shows excellent selectivity, avoiding generation over alkylated byproducts.