A variety of pseudorutaecarpine derivatives were prepared in good to excellent yields through a gold(I)-catalyzed selective cyclization and 1,2-shift of N-alkynyl quinazolinone-tethered indoles. Mechanistic study revealed that spiroindolenines generated in situ by cyclization at the the indole C3 position underwent an alkenyl 1,2-shift to generate pseudorutaecarpine. The reaction proceeds under mild

The rhodium(III)-catalyzed C‒H bond activation and vinylene transfer of enaminones with vinylene carbonate have been proposed for the synthesis of substituted 1-hydroxy-2-naphthaldehydes in 49–84% yields. Several preliminary mechanistic studies and hydroxyl-directed derivatization reactions of 1-hydroxy-2-naphthaldehydes were also performed. This method offers an alternative approach for the synthesis

Fluorine-containing moieties are widely used in the pharmaceutical, agrochemical, and material fields. Thus, these structures are of immense interest in the fields of organic synthesis and medicinal chemistry. Among various fluorinated groups, the difluoromethyl unit has drawn increasing attention due to its unique pharmaceutical properties. In recent years, several methods for the synthesis of difluoromethylated

A route for the construction of all-carbon tetra-substituted olefins through visible-light promoted coupling of diazo compounds with iodonium ylides was developed. A wide range of all-carbon tetra-substituted olefins was obtained in moderate to good yields. The synthetic values of the current method were further approved by the synthesis of natural isolates modified alkenes and the successful transformation

The direct carboxylation of inert aryl C–H bond catalyzed by abundant and cheap nickel is still facing challenge. Herein, we report the Ni-catalyzed direct carboxylation of aryl C–H bonds in benzamides under 1 atm of CO2 to afford various methyl carboxylates or phthalimides, dealing with different post-processing. The reaction displays excellent functional group tolerance and affords moderate to high

A variety of chiral nine-membered N-heterocycles were prepared in moderate to good yields with high diastereoselectivity through a silver(I)-catalyzed [3+2] cycloaddition and [3,3]-rearrangement of N-vinyl-α, β-unsaturated nitrones and chiral 3-propioloyloxazolidin-2-ones. Experimental studies showed that silver catalyst promoted the cycloaddition and rearrangement process, and the stereochemistry

A one-pot protocol for constructing 1,4-difunctionalized quinoline/pyridine derivatives via the reaction of N-heteroaromatics, alkyl halides, and active methylene/methyl compounds was developed. The transformation involves dearomative functionalization of an in situ-activated N-heteroaromatic to construct new C–N and C=C bonds. This reaction has a broad substrate scope and functional group tolerance

Employing anilines as nucleophiles in double carbonylation is a longstanding challenge. In this communication, a Mn(III)-promoted double carbonylation of alkylborates or Hantzsch esters with anilines toward the synthesis of α-ketoamides has been developed. By using easily available potassium alkyltrifluoroborates or Hantzsch esters as the starting material, and cheap and non-toxic Mn(OAc)3·2H2O as

We report the enantiodivergent reaction of ketimines derived from α-ketoesters with malononitriles using a single chiral source. The reactions using an 8-quinolinesulfonyl cinchona alkaloid catalyst in the presence and absence of Et2Zn gave both enantiomers in high yields with high enantioselectivities (53~99% yield, 99:1~3:97 er). The obtained malononitrile-derived α-amino acids were converted into

Pentasubstituted pyrrolidines are ubiquitous constituents of natural products and drugs, however the access options to them especially with respect to absolute and relative stereochemistry are not well developed. We report an asymmetric synthesis of N,2,3,4,5-pentasubstituted pyrrolidines by oxidative single-electron transfer-catalyzed tandem aza-Michael addition/radical 5-exo cyclization/oxygenation

Decomposition of donor-acceptor diazo compounds leads to the formation of reactive carbene intermediates. These can undergo a wide variety of carbene transfer reactions to yield synthetically useful products. Herein, we report a highly selective borane catalyzed cyclization reaction from the combination of two different diazo compounds to afford N-substituted pyrazoles. The selective decomposition

A self-photocatalyzed sulfonylation/cyclization of quinazolinones containing unactivated alkenes with various sulfonyl chlorides was developed. The protocol provides access to sulfonyl radicals via energy transfer from the quinazolinone skeleton to the sulfonyl chloride. Notably, the transformations proceeded without any external photocatalysts, additives, or oxidants, providing an alternative method

A readily accessible organic-inorganic hybrid catalyst is reported for the reductive fragmentation of α-halocarbonyl compounds. The robust hybrid catalyst is a self-stabilizing combination of ZnCl2 Lewis acid and acridine orange as the photoactive organic dye. Mechanistic specifics of this hybrid catalyst have been studied in detail using both photophysical and electrochemical experiments. A systematic

Dearomative ring expansion/spirocyclization of indole-2-carboxylates with propargylic alcohols bearing electron-withdrawing aromatic groups in the presence of PTSA leading to spiro[benzo[b]oxazine-furans via oxygen insertion along with dihydrocyclopenta[e]indole-2-carboxylates is developed; the same reactants under moderately high temperatures, afford fused pyrano-indolones. In contrast, copper(II)

C–H arylation of 1-pyrenylphosphine derivatives catalyzed by rhodium and directed by a diphenylphosphino group is selectively achieved at the K-region, i.e. 4-, 5-, 9-, or 10-position of the pyrene moiety. The functionalization at the K-region of topical pyrene substrates is hardly accessible by conventional organic synthetic methods. This peri C–H activation/arylation of pyrenes using (hetero)aryl

Hydroxamic acids are metal-chelating compounds that show important biological activity including anti-tumor effects. We have recently engineered the transketolase from Geobacillus stearothermopilus (TKgst) to convert benzaldehyde as a non-natural acceptor substrate. Realizing the structural and electronic similarity to nitrosobenzene, we studied the TK-catalyzed conversion of nitrosoarenes to yield