An elegant approach to quaternary oxindole formation has been developed through a room temperature decarboxylation/radical C-H functionalization by visible-light photoredox catalysis.

Abstract The construction of an aryl ketone structural unit by means catalytic carbon–carbon coupling reactions represents the state-of-the-art in organic chemistry. Herein we achieved direct deoxygenative synthesis aqueous solution from readily available aromatic carboxylic acids and alkenes, affording structurally diverse ketones moderate to good yields. Visible-light photoredox catalysis enables deoxygenation as acyl sources with triphenylphosphine a distinct perspective on activation....

Trifluoromethylation/arylation: N-aryl acrylamides undergo visible-light-induced tandem trifluoromethylation/arylation in the presence of a ruthenium photocatalyst with Togni's reagent as CF3 source (see scheme). This reaction serves powerful and ecofriendly synthetic method for preparation variety CF3-containing oxindoles bearing quaternary carbon center.

We report a general, practical, and scalable means of preparing deuterated aldehydes from aromatic aliphatic carboxylic acids with D2 O as an inexpensive deuterium source. The use Ph3 P O-atom transfer reagent can facilitate the deoxygenation acids, while Ph2 POEt is better for acids. highly precise complex makes this protocol promising late-stage deoxygenative deuteration natural product derivatives pharmaceutical compounds.

Abstract Density functional theory (DFT) investigations revealed that 4‐cyanopyridine was capable of homolytically cleaving the B−B σ bond diborane via cooperative coordination to two boron atoms generate pyridine boryl radicals. Our experimental verification provides supportive evidence for this new activation mode. With novel strategy, we have experimentally realized catalytic reduction azo‐compounds hydrazine derivatives, deoxygenation sulfoxides sulfides, and quinones with B 2 (pin) at...

Abstract The synthesis of all-carbon tetrasubstituted olefins under mild reaction conditions is challenging because the inevitable issues including significant steric hindrance and uncontrolled Z/E stereoselectivity. In this paper, we report alkenes from readily available carboxylic acids alkenyl triflates with synergistic catalysis cyclo-octa-1,5-diene(tetramethyl-1,4-benzoquinone)nickel visible light an air atmosphere, thus avoiding need for a glovebox or Schlenk line. A wide range...

An organocatalytic cascade reaction that involves the formation of C-N, C-O and C=N bonds in one process via dual sp(3) C-H activation has been developed. This protocol affords a facile metal-free methodology for synthesis oxazole derivatives air under mild conditions.

A breath of fresh air: The title reaction has been developed for the coupling amines with nitroalkanes and different unmodified ketones using air as sole oxidant under mild conditions. safe, convenient, environmentally benign process, well low catalyst loading, short time, good yields make this protocol very practical (see scheme). Detailed facts importance to specialist readers are published "Supporting Information". Such documents peer-reviewed, but not copy-edited or typeset. They made...

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...

A new synthetic approach toward direct C–N bond formation through sp3 C–H activation has been developed under metal-free conditions. Both primary and secondary benzylic substrates could react smoothly with various amines to give only mono-amination products good excellent yields.

Oxidative α-cyanation of tertiary amines is catalyzed by gold complexes with trimethylsilyl cyanide to afford the corresponding α-aminonitriles in presence tert-butyl hydroperoxide good excellent yields under acid-free conditions at room temperature.

The trifluoromethyl-substituted anilines are biologically active compounds and useful building blocks. In this communication, we have developed the first visible-light-induced radical trifluoromethylation of free with commercially available easily handled Togni reagent at room temperature. resulting products were successfully transformed into a variety valuable fluorine-containing molecules heterocyclic compounds. This protocol provides an economical powerful route to trifluoromethylated anilines.

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...

A copper-mediated C2-cyanation of indoles using cheap and commercially available acetonitrile as the "nonmetallic" cyanide source was achieved through sequential C-C C-H bond cleavages. The installation a removable pyrimidyl group on indole nitrogen atom is key for this C2 selectivity. This approach provides novel alternative route leading to indole-2-carbonitrile.

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...

A palladium-catalyzed decarboxylative C2-acylation of indoles with α-oxocarboxylic acids was achieved. This protocol represents a novel and complementary approach to 2-aroylindoles.

The bicyclic isoxazolidine scaffolds are the ubiquitously recurring motifs in alkaloids. Despite of their facile biosynthesises nature, laboratory synthesis these derivatives is still complicated. In this paper, concisely constructed one process with excellent stereoselectivity from simple tertiary amines through a C–H activation-retro-aza-Michael-oxidation-cyclization tandem sequence by means visible-light. This protocol provides concise approach to dactylicapnosinine derivatives.

The first transition-metal-free, site-specific umpolung trifluoromethylthiolation of tertiary alkyl ethers has been developed, achieving the challenging C(sp3 )-SCF3 coupling under redox-neutral conditions. synergism organophotocatalyst 4CzIPN and BINOL-based phosphorothiols can site-selectively cleave sp3 )-O ether bonds in complex molecules initiated by a polarity-matching hydrogen-atom-transfer (HAT) event. incorporation several competing benzylic methine )-H little influence on...

Abstract The ketone functional group has a unique reactivity in organic chemistry and is associated with number of useful reactions. Catalytic methods for synthesis are continually being developed. Here, we report photoredox, nickel phosphoranyl radical synergistic cross-electrophile coupling commercially available chemicals, aromatic acids aryl/alkyl bromides. This allows concise highly functionalized ketones directly, without the preparation activated carbonyl intermediates or...

Abstract The benzylic positions in drugs are sites that readily react with cytochrome P450 oxidases via single-electron oxidation. New synthetic methodologies to incorporate a fluoroalkyl group at the site continually being developed, and this paper, we report metal-free site-selective organophotoredox-catalyzed trifluoromethylthiolation of C-H bonds for wide variety alkyl arenes heteroarenes. precise predictive regioselectivity among various C(sp 3 )-H originates from an inner-sphere...