Abstract Asymmetric functionalization of aromatic CH bonds N,N‐disubstituted anilines with diazo compounds and imines is reported for the efficient construction α,α‐diaryl benzylic quaternary stereocenters in good yields high diastereoselectivities excellent enantioselectivities. This Rh II /chiral phosphoric acid cocatalyzed transformation proposed to proceed through a metal‐carbene‐induced zwitterionic intermediate which undergoes electrophilic trapping. To best our knowledge, this first...

Abstract Enantioselective α -aminomethylation of carbonyl compounds constitutes a powerful protocol for introducing aminomethyl groups to simple organic molecules. However, current strategies rely on nucleophile-based enantioselective activation with inherently activated substrates only, and based the in situ-generated unstable formaldimines remains elusive, probably owing their nature lack steric environment efficient stereocontrols. Here, rhodium/chiral phosphoric acid cooperative...

The N-N bond is widely found in natural products and bioactive compounds.The atropisomerism of bond, however, has been dismissed for a long time due to the stereotype that axis unstable.The electronic barrier stemming from repulsive interaction between lone pairs on two nitrogen atoms leads rotationally hindered axis, resulting stable atropisomers.Since first report 2021, catalytic asymmetric synthesis atropisomers developed rapidly into an emerging area.These reactions include N-H...

An efficient kinetic resolution of racemic trans-2,3-aziridinyl alcohols is established via zinc catalyzed ring opening reactions with various amines as the nucleophiles. The directing effect hydroxyl group and precise enantiodiscrimination by dinuclear cooperative catalyst are keys to success high regioselectivity enantioselectivity. A range enantioenriched vicinal diamines were obtained in good yields excellent ee values. To best our knowledge, this first example directed enantioselective...

Abstract The catalytic asymmetric dearomatization (CADA) reaction has proved to be a powerful protocol for rapid assembly of valuable three-dimensional cyclic compounds from readily available planar aromatics. In contrast the well-studied indoles and naphthols, phenols have been considered challenging substrates intermolecular CADA reactions due combination strong aromaticity potential regioselectivity issue over multiple nucleophilic sites (O, C2 as well C4). Reported herein are chiral...

Abstract We report herein an enantioselective [3+3] annulation of indoline‐2‐thiones with yne–enones by chiral dinuclear zinc catalysts via a Brønsted base and Lewis acid cooperative activation model. This transformation proceeded through sequential conjugate addition, allenyl ketone formation intramolecular sulfa‐Michael 6‐ endo ‐trig cyclization. A range enantioenriched tetrahydrothiopyrano[2,3‐ b ]indole derivatives bearing exocyclic double bond were obtained in moderate yields excellent...

Abstract An unprecedented catalytic asymmetric allylation of isatins and isatin‐derived ketimines is reported enabled by a gold chiral organocatalyst cooperative catalysis strategy. This method offers expeditious access to 2,5‐disubsituted alkylideneoxazolines containing vicinal stereogenic centers, mainly in optically pure form, which are otherwise impossible access. Mechanistic evidence reveals the presence an alkylgold intermediate, X‐ray crystal structure allylgold species illuminates...

With a dinuclear zinc-ProPhenol complex as catalyst, an efficient and novel [3 + 3] annulation of indoline-2-thiones isatylidene malononitriles has been successfully developed via the Brønsted base Lewis acid cooperative activation model. This practical methodology gives access to broad range chiral spiro[indoline-3,4′-thiopyrano[2,3-b]indole] derivatives in good yields with excellent levels enantioselectivities (up 88% yield 99% ee).

Abstract Herein, the first diversity‐oriented catalytic asymmetric dearomatization of indoles with o ‐quinone diimides ( ‐QDIs) is reported. The (CADA) one research focuses in terms structural and biological importance dearomatized indole derivatives. Although great achievements have been made target‐oriented CADA reactions, reactions are regarded as more challenging remain elusive due to lack synthons featuring multiple reaction sites difficulty precise control chemo‐, regio‐,...

Abstract The oxirane and aziridine rings are valuable building blocks in modern synthetic chemistry catalytic asymmetric ring opening reactions of these three membered systems have emerged as a powerful chemical tool for the synthesis natural products biologically active compounds. In this context, regioselective ring‐opening structurally or electronically unbiased epoxides aziridines is challenging. Recently, metal‐catalyzed substrate directed strategies successfully applied regio‐...

Developing an efficient and highly enantioselective protocol to access homopropargyl amines is of high interest the synthetic community also remains a formidable challenge for organic chemists. Here, we present integrated Rh2(OAc)4- BINOL-derived chiral phosphoric acid cooperatively catalyzed three-component reactions alkynyldiazoacetates, imines with various nucleophiles including alcohols, indoles, N,N-disubstituted anilines, affording corresponding containing two vicinal centers in...

An enantioselective cyclization of diazoindolinones with o-hydroxymethyl chalcones has been established by a cooperative dirhodium complex and chiral phosphonic acid catalysis under mild conditions. This reaction is the first example catalytic asymmetric intramolecular Michael-type trapping oxonium ylide enabled phosphoric through dual H-bonding activation model, which provides an efficient access to spirochroman-3,3-oxindoles, vicinal quaternary tertiary stereocenters, in good excellent...

Highly enantioselective formal [3 + 2] cycloaddition via a Brønsted base and Lewis acid cooperative activation model.

The application of dinuclear zinc catalysts in a dearomatization reaction has been developed. Catalytic asymmetric [3+2] annulations 2-nitrobenzofurans or 2-nitrobenzothiophenes with CF3 -containing N-unprotected isatin-derived azomethine ylides catalyzed by are realized excellent diastereomer ratios (dr) >20 : 1 and enantiomeric excess (ee) up to 99 %. This protocol provides practical, straightforward access structurally diverse pyrrolidinyl spirooxindoles containing...

The Sc(III)-catalyzed [2,3]-sigmatropic rearrangement of sulfonium ylides derived from azoalkenes has been established. Owing to the absence a carbenoid intermediate, this protocol represents first non-carbenoid variant Doyle-Kirmse reaction. Under mild conditions, variety tertiary thioethers have readily prepared in good excellent yields.

Reported herein is the catalytic asymmetric aminative dearomatization reaction of common phenols. As opposed to well-studied indoles and naphthols, phenols are supposed be challenging substrates for reactions in terms their strong aromaticity regioselectivity issues. Under catalysis a chiral phosphoric acid, C4-regiospecific with azodicarboxylates readily occurred at ambient temperature, delivering an array biologically synthetically important aza-quaternary carbon cyclohexadieneones good...

This study introduces a novel approach for synthesizing Benzoxazine-centered Polychiral Polyheterocycles (BPCPHCs) via an innovative asymmetric carbene-alkyne metathesis-triggered cascade. Overcoming challenges associated with intricate stereochemistry and multiple chiral centers, the catalytic Carbene Alkyne Metathesis-mediated Cascade (CAMC) is employed using dirhodium catalyst/Brønsted acid co-catalysis, ensuring precise stereo control as validated by X-ray crystallography. Systematic...

Abstract Asymmetric functionalization of aromatic CH bonds N,N‐disubstituted anilines with diazo compounds and imines is reported for the efficient construction α,α‐diaryl benzylic quaternary stereocenters in good yields high diastereoselectivities excellent enantioselectivities. This Rh II /chiral phosphoric acid cocatalyzed transformation proposed to proceed through a metal‐carbene‐induced zwitterionic intermediate which undergoes electrophilic trapping. To best our knowledge, this first...

A zinc-catalyzed intermolecular alkyne–carbonyl metathesis reaction of ynamides with isatins followed by an amide to ester conversion has been developed, which produces the indolone derivatives a fully substituted alkene species in good high yields. The salient features this include following: mild conditions, inexpensive zinc catalyst, broad substrate scope, excellent regiocontrol and stereoselectivity, amenable gram scale.

The C(sp2)–H function of indole ketone with diazo compound via a rhodium(II)-catalyzed intramolecular electrophilic trapping reaction under mild conditions in air was demonstrated. established methodology provided highly efficient approach for direct synthesis mutisubstituted tetrahydrocarbazoles continuous quaternary carbons. resulting products facilitate further modification to conveniently construct additional fused heterocyclic rings. By phenotypic screening, several exhibit good...

The umpolung activity of hemiacetals serving as α-carbon nucleophiles has been reported via dinuclear zinc cooperative catalysis. This strategy applied to catalytic asymmetric tandem reactions 1-tosylindoline-2,3-diols with β,γ-unsaturated-α-keto compounds, providing a broad series structurally diverse tetrahydrofuran spirooxindoles and dihydrofurans, respectively. In addition, products could be transformed quinazoline quinoline derivatives.

A highly atom-economical and novel enantioselective [3 + 2] spiroannulation reaction of saccharine-derived cyclic 1-azadienes with α-hydroxy-1-indanones has been developed.

This is an efficient asymmetric Michael/lactonization cascade reaction via a Brønsted base and Lewis acid cooperative activation model.

We described herein a neoteric enantioselective cascade Michael/acyl transfer reaction of enynones and α-hydroxy aryl ketones catalyzed by dinuclear zinc cooperative catalysis. A series structurally diverse chiral 1,5-dicarbonyl compounds were synthesized in good yields with excellent stereoselectivities. This strategy features broad substrate scope, high atom economy, as well efficient electrophilic acyl reagents asymmetric reactions for the first time.