Manganese-catalyzed hydrogenation reactions have attracted broad interest since the first report in 2016. Among reported catalytic systems, Mn catalysts supported by tridentate PNP- and NNP-pincer ligands most commonly been used. For example, a number of PNP-Mn pincer for aldehydes, aldimines, ketones, nitriles, esters. Furthermore, various NNP-Mn shown to be active less-reactive substrates such as amides, carbonates, carbamates, urea derivations. These observations indicated that exhibit...

Abstract Transition-metal-catalyzed direct site-selective functionalization of arene C–H bonds has emerged as an innovative approach for building the core structure pharmaceutical agents and other versatile complex compounds. However, para -selective seldom been explored, only a few examples, such steric-hindered arenes, electron-rich substrates with directing group, have reported to date. Here we describe development ruthenium-enabled difluoromethylation anilides, indolines,...

A highly para-selective CAr -H difluoromethylation of ketoxime ethers under ruthenium catalysis has been developed. wide variety are compatible with the reaction, which leads to corresponding para-difluoromethylated products in moderate good yield. mechanistic study clearly showed that chelation-assisted cycloruthenation is key factor para selectivity ethers. Density functional theory was used gain a theoretical understanding selectivity.

Disclosed herein is a versatile and practical strategy for catalytic radical dearomatization. By means of this strategy, we realized the trifluoromethylative dearomatization indoles furans with CO2 via Cu catalysis. We also demonstrated C-3 C–O bond formation to generate spirocyclic indolines. A variety important CF3-containing indolines spiroacetals can be synthesized atmospheric under mild reaction conditions. Moreover, these multicomponent reactions feature high selectivity, good...

Direct construction of fully alkyl-substituted tertiary chiral centers remote to activating groups is highly challenging and desirable. Herein, a Ni-catalyzed enantioselective hydroalkylation unactivated alkenes with alkyl halides at room temperature reported, providing general practical access stereogenic carbon not adjacent groups. This reaction undergoes the regio- stereoselective hydrometalation nontrivial Markovnikov selectivity, followed by cross-coupling electrophiles trialkyl...

A novel chiral phosphine–urea bifunctional ligand has been developed for Cu-catalyzed asymmetric 1,3-dipolar cycloaddition of iminoesters with methacrylonitrile, a long-standing challenging substrate in catalysis. Distortion–interaction energy analysis based on density functional theory (DFT) calculations reveals that the distortion plays an important role observed enantioselectivity, which can be attributed to steric effect between phosphine and dipole reactant. DFT also indicate...

Transition metal-catalyzed addition of diaryl alkynes with arylating reagents for the synthesis tetraarylethylenes generally encounters rigorous reaction conditions and relies on use prefunctionalized substrates such as organic halides or surrogates organometallic reagents. In this work, we establish a highly trans-selective 1,2-diheteroarylation azoles via rhodium/copper cocatalyzed C–H addition/oxidative coupling process. Moreover, diheteroarylation developed herein could open door...

Here we report that a palladium(0) complex can mediate the unprecedented intermolecular coupling reaction of 1,3-enynes and N-sulfonylimines regio- stereoselectively, resultant palladium(II) species undergo cascade Suzuki with organoboronic reagents. The substrate scope is substantial for asymmetric three-component process, enantioenriched all-carbon tetra-substituted alkene derivatives are efficiently constructed in modular cis-difunctionalized manner. Control experiments density functional...

A novel class of alkyne-tethered amides facilitates an unprecedented photoinduced palladium-catalyzed radical relay formal [5 + 2] reaction. This innovative strategy allows for the rapid construction diverse fused benzoazepine structures, yielding structurally and compelling compounds. With a broad substrate scope excellent functional group tolerance, methodology synthesizes biologically active Notably, resulting tricyclic benzo[b]azepines offer diversification opportunities through simple...

We propose a novel Cu(<sc>i</sc>)–Cu(<sc>ii</sc>) catalytic cycle for the copper-catalyzed oxytrifluoromethylation of allylamines with CO₂, which proceeds through radical–radical cross-coupling pathway.

Computational characterization of the oxidation addition promoted in rhodium-catalyzed cyclopropenone activation and conversion via quinolyl-, pyridyl-, nitrone-directed C–H is presented. Our theoretical studies found that a common catalytic cycle for these reactions starts with Rh(III)-mediated concerted metalation–deprotonation or electrophilic deprotonation to afford aryl-Rh(III) intermediate. Oxidative then gives cyclorhoda(V)butanone intermediate, leading cleavage cyclopropene moiety...

Carboxylic acids are not readily applied as carbon-based nucleophiles due to their intrinsic acidic group. Here, we demonstrate that free (E,E)-2,4-dienoic form electron-neutral and highest occupied molecular orbital-raised η2-complexes with Pd(0) undergo Friedel–Crafts-type additions imines exclusive α-regioselectivity, giving formal dienylated products after decarboxylation. Unusual switchable (E,E)- (Z,E)-selectivity, along excellent enantioselectivity, is achieved via ligand-controlled...

As a general mechanism proposal, Pd(ii)-H migration insertion process is not able to well explicate the Pd-catalyzed hydroamination of amines and 1,3-dienes. Here we demonstrate that 1,3-dienes form electron-neutral HOMO-raised η2-complexes with Pd(0) via π-Lewis base activation, which undergoes protonation variety acidic sources, such as Brønsted acids, Lewis acid-activated indazoles, Pd(ii) pre-catalyst triggered ammonium salts. The resultant π-allyl palladium complexes undergo amination...

The alkenylation reaction of propargylic derivatives catalyzed by transition metals represents a powerful synthetic strategy, usually in double attack mode to access multifunctional cyclic products. While few asymmetric reactions via palladium catalysis have been uncovered, here we report non-precious Ni(0)-based chiral complex exhibits superior efficacy the assemblies diversity carbonates and vinylogous donors. proceeds consecutive activations nucleophiles, finally giving (3 + 2) annulation...

Regio- and stereoselective photoredox-catalyzed cyclizations of alkene-substituted β-ketoesters have been accomplished for the synthesis polyfunctionalized cyclopentanones. This was achieved using 2,3,5,6-tetrakis(carbazol-9-yl)-1,4-dicyanobenzene (4CzTPN) 2,4,6-triisopropyl-thiophenol as cocatalysts under illumination a blue-light-emitting-diode at ambient temperature. The developed chemistry successfully applied in enantioselective total tricyclic prostaglandin D2 metabolite...

Here we present an enantioselective intramolecular hydroamination reaction of o-aminophenyl-1,3-enynes via cooperative catalysis Pd(0) and chiral phosphoric acid. This approach enables the efficient construction N–N/C–N axially stereogenic indoles with broad skeletal diversity high levels enantioselectivity in a completely atom-economic manner. Mechanistic studies indicate that protonation alkyne moiety π-Lewis base activation is favored, phosphate counteranion plays crucial role controlling...

An in-depth theoretical study of synergistic Cu(II)/Cu(I)-mediated alkyne coupling was performed to reveal the detailed mechanism for C–C bond formation, which proceeded via an unusual dinuclear 1,2-reductive elimination. Because reactant elimination calculated be triplet while products were singlet, minimum energy crossing point (MECP) introduced Cu/TMEDA/alkyne system clarify spin between state and singlet potential surfaces. Computational results suggest that C–H cleavage solely catalyzed...

Terminal alkynes have become one of the most versatile building blocks for C–C bond construction in past few decades, and they are usually considered to convert acetylides before further transformations. In this study, a novel direct nucleophilic addition mode Cu(I)-catalyzed cross-coupling terminal N-tosylhydrazones synthesize chiral allenes is proposed, it was investigated by density functional theory with M11-L functional. Three different reaction pathways were investigated. The...

An annulation cascade of arylnitriles with alkynes is disclosed to provide stable delocalized carbocations the ability specifically target lysosomes.

We report the first example of Rh(II) -catalyzed chemoselective double C(sp(3) )-H oxygenation, which can directly transform various toluene derivatives into highly valuable aromatic aldehydes with great chemoselectivity and practicality. The critical combination catalyst Rh(OAc)2 , oxidant Selectfluor, solvents TFA/TFAA promises successful delivery oxidation satisfactory yields. A possible mechanism involving a unique carbene-Rh complex is proposed, has been supported by both experiments...

Abstract Transition metal-catalyzed radical–radical cross-coupling reactions provide innovative methods for C–C and C–heteroatom bond construction. A theoretical study was performed to reveal the mechanism selectivity of copper-catalyzed C–N reaction. The concerted coupling pathway, in which a is formed through direct nucleophilic addition carbon radical nitrogen atom Cu(II)–N species, demonstrated be kinetically unfavorable. stepwise involves combination with species before formation, shown...

A novel bifunctional phase-transfer catalyst <bold>1i</bold> was found to be highly efficient for the nitro-Mannich reaction of unactivated ketone-derived imines with introduction protecting group 6-methyl-2-pyridylsulfonyl ketimines. Density functional theory (DFT) calculations are also performed give possible transition-state model.