The first enantioselective organocatalytic two- and three-component reactions via a domino Knoevenagel/Michael/cyclization sequence with cupreine as catalyst have been developed. A wide range of optically active spiro[4H-pyran-3,3′-oxindoles] were obtained in excellent yields (up to 99%) good enantioselectivities 97%) from simple readily available starting materials under mild reaction conditions. These heterocyclic spirooxindoles will provide promising candidates for chemical biology drug discovery.

Chiral amines are widely used as catalysts in asymmetric synthesis to activate carbonyl groups for α-functionalization. Carbonyl catalysis reverses that strategy by using a group primary amine. Inspired biological catalysis, which is exemplified reactions of pyridoxal-dependent enzymes, we developed an N-quaternized pyridoxal catalyst the Mannich reaction glycinate with aryl N-diphenylphosphinyl imines. The exhibits high activity and stereoselectivity, likely enabled enzyme-like cooperative...

Abstract Palladium‐catalyzed decarboxylative cycloadditions have emerged as highly effective methods for constructing structurally diverse carbo‐ and heterocycles because of the formation at least two carbon‐carbon or carbon‐heteroatom bonds in a single step. It is great interest to chemists that this type cycloaddition reactions possesses some special advantages such high reactivity, exclusive regioselectivity, good functional group compatibility. Based on these qualities,...

This paper describes a catalytic asymmetric diamination process using di-tert-butyldiaziridinone as nitrogen source with catalyst generated from Pd2(dba)3 and chiral phosphorus amidite ligand. A wide variety of conjugated dienes triene can be effectively diaminated in good yields high regio-, diastereo-, enantioselectivities.

The first example of a direct catalytic asymmetric intermolecular aldol reaction 3-isothiocyanato oxindoles to simple ketones with bifunctional thiourea-tertiary amine as catalyst is reported. This strategy provides promising approach for the synthesis range enantioenriched spirocyclic bearing two highly congested contiguous tetrasubstituted carbon stereocenters. Versatile transformations oxindole products into other structurally diverse have also been demonstrated.

This paper describes a novel diamination process of terminal olefins at allylic and homoallylic carbons via formal C−H activation using di-tert-butyldiaziridinone as nitrogen source Pd(PPh3)4 catalyst. A wide variety can be effectively diaminated in good yields with high stereoselectivity.

A wide range of structurally diverse 3,3′-thiopyrrolidonyl spirooxindoles bearing three contiguous stereogenic centers can be smoothly obtained via a domino Michael/cyclization reaction between 3-isothiocyanato oxindoles and 3-methyl-4-nitro-5-alkenyl-isoxazoles with commercially available quinine as the catalyst under mild conditions. The protocol is significantly characterized by high reactivity, low loading (1 mol %), an excellent diastereo- enantioselectivity (up to >99:1 dr 98% ee).

Abstract Highly enantioselective [3+2] coupling of 3‐substituted indoles with quinone monoimines promoted by a chiral phosphoric acid has been reported. A large variety benzofuroindolines were prepared in moderate to good yields (up 98 %) generally excellent enantioselectivities 99 % ee ).

An efficient FeCl3-catalyzed stereoselective intramolecular tandem 1,5-hydride transfer/ring closure reaction was developed. The method allows for the formation of structurally diverse spirooxindole tetrahydroquinolines in high yields (up to 98%) with good excellent levels diastereoselectivity 99:1 dr). catalytic enantioselective variant this process also investigated preliminarily a chiral BINOL-derived phosphoric acid.

An unprecedented organocatalytic asymmetric Michael/cyclization cascade reaction of 3-isothiocyanato oxindoles and 3-nitroindoles has been disclosed. A wide range enantioenriched polycyclic spirooxindoles, containing three contiguous chiral centers with two them having quaternary stereocenters, could be smoothly obtained satisfactory results (up to 99% yield, >99:1 dr, 96% ee). This method is very promising because the scalable, versatile transformations products into other spirocyclic are...

Abstract The first organocatalytic diastereo‐ and enantioselective Michael addition reaction of 4‐substituted‐pyrazolin‐5‐ones to nitroolefins has been developed with a chiral bifunctional thiourea as organocatalyst. A wide variety desired multi‐substituted pyrazolin‐5‐one derivatives contiguous quaternary tertiary stereocenters are smoothly obtained in very good yields (up 98%) excellent enantioselectivities to>99% ee ) acceptable diastereoselectivities 80:20). This experimentally simple...

A catalytic asymmetric Michael/cyclization cascade reaction of 3-isothiocyanato oxindoles and 3-nitroindoles has been disclosed with a chiral Zn(OTf)2/diphenylamine-linked bis(oxazoline) complex as the catalyst. range enantioenriched polycyclic spirooxindole derivatives containing three contiguous stereocenters were efficiently constructed in quantitative yields excellent diastereo- enantioselectivities. Importantly, metal strategy this work is significantly superior to previous...

An efficient and stereoselective reaction between 3-isothiocyanato oxindoles isatins/isatinimines has been developed to afford structurally diverse dispiro[oxazolidine-2-thione]bisoxindoles dispiro[imidazolidine-2-thione]bisoxindoles in excellent results under mild conditions. The potential of asymmetric induction by means a chiral auxiliary was explored. isomers are separable, products could be isolated as single diastereomers column chromatography. Further synthetic transformations the...

Cascading catalysis: 3-Isothiocyanato oxindoles act as powerful and versatile precursors for a range of structurally diverse dispirocyclic thiopyrrolidineoxindoles containing two spiro-quaternary three contiguous stereogenic centers in quantitative yields with excellent disatereo- enantioselectivities by only using 1 mol % amino-thiocarbamate catalyst. As service to our authors readers, this journal provides supporting information supplied the authors. Such materials are peer reviewed may be...

Enantioselective dearomative [3 + 2] cycloaddition reaction of 2-nitrobenzofurans with 3-isothiocyanato oxindoles was developed. The employs a chiral bis(oxazoline)/Zn(OTf)2 catalyst, allowing practical, straightforward access to structurally diverse spirooxindoles containing 2,3-dihydrobenzofuran motif and three contiguous stereocenters excellent diastereo- enantioselectivities. synthetic potentials the method have been demonstrated by scale-up experiment transformations products....

N-2,2,2-Trifluoroethylisatin ketimines with β-trifluoromethyl enones, 3-trifluoroethylidene oxindole, and benzofuranone can undergo asymmetric [3 + 2] cycloaddition, catalyzed by chiral bifunctional squaramide-tertiary amine catalysts, affording a wide spectrum of 3,2'-pyrrolidinyl spirooxindoles. The significance this protocol is highlighted its extremely high efficiency in the construction structurally diverse spirocyclic oxindoles, bearing vicinally bis(trifluoromethyl)-substituted...

The first organocatalyzed asymmetric dearomative cycloaddition between 2-nitrobenzofurans and isatin-derived Morita-Baylis-Hillman carbonates has been developed. Using a modified cinchona alkaloid as the catalyst, series of structurally diverse cyclopenta[ b]benzofuran derivatives with three contiguous stereocenters, including spiro-quaternary chiral center, could be smoothly obtained in excellent results (all cases >20:1 dr, up to 99% yield 98% ee). utility this method was showcased by...

A copper-catalyzed diastereo- and enantioselective decarboxylative [3 + 2] cyclization reaction of alkyne-substituted cyclic carbamates with azlactones has been established. range optically pure γ-butyrolactams bearing two vicinal tetrasubstituted carbon stereocenters were obtained in high yields good to excellent stereoselectivities (up 99% yield, 99:1 dr, ee). This is the first example asymmetric synthesis containing sterically congested via a pathway.

This study demonstrates a highly efficient regiodivergent ligand-controlled palladium-catalyzed cycloaddition reaction of vinyloxazolidine-2,4-diones with 1,3,5-triazinanes. In the presence diphosphine ligand, proceeds via (5+2) pathway to afford 1,3-diazepin-4-ones in excellent yields, while using monophosphine smoothly (3+2) give imidazolidin-4-ones good yields.

A highly diastereo- and enantioselective Michael addition reaction with respect to prochiral 3-substituted oxindoles maleimides by a chiral bifunctional thiourea−tertiary amine catalyst was investigated for the first time. The corresponding adducts, containing quaternary center at C3-position of oxindole as well vicinal tertiary center, were generally obtained in good high yields (up 92%) excellent 99:1 dr) enantioselectivities 99% ee).

A Cu(I)-catalyzed asymmetric diamination for a variety of conjugated dienes and triene with encouraging ee’s has been effectively achieved using (R)-DTBM-SEGPHOS as chiral ligand di-tert-butyldiaziridinone the nitrogen source.

This paper describes a novel intermolecular diamination process with CuCl as catalyst and di-tert-butylthiadiaziridine 1,1-dioxide nitrogen source. A variety of activated terminal olefins can be effectively diaminated in good yields under mild reaction conditions.

A bifunctional thiourea-tertiary amine-catalyzed asymmetric hydroxymethylation of 3-substituted oxindoles using paraformaldehyde as the C1 unit was developed. wide scope oxindoles, bearing C3 sterically congested quaternary carbon centers, were smoothly obtained in good to excellent yields (up 99%) and high enantioselectivities 91% ee) under mild reaction conditions. more significant feature this approach employs cheap readily available a unit, which is activated by chiral thiourea organocatalysts.

By design: A series of α-acetoxy-β-enamino esters 1 were synthesized and then subjected to catalytic asymmetric hydrosilylation. In the presence a chiral Lewis base catalyst, reactions proceeded smoothly provide wide range α-acetoxy β-amino acid derivatives in high yields with good diastereoselectivities enantioselectivities.