Abstract The 3,3′‐disubstituted oxindole structural motif is a prominent feature in many alkaloid natural products, which include all kinds of tetrasubstituted carbon stereocenters, spirocyclic or not, all‐carbon heteroatom‐containing. catalytic asymmetric synthesis the stereocenter at C‐3 position framework integrates new synthetic methods and chiral catalysts, reflects latest achievements catalysis, facilitates sufficient quantities related compounds as potential medicinal agents...

3,3-Disubstituted oxindoles are widely distributed in natural products, drugs, and pharmaceutically active compounds. The absolute configuration the substituents on fully substituted C3 stereocenter of oxindole often significantly influence biological activity. Therefore, tremendous efforts have made to develop catalytic enantioselective syntheses this prominent structural motif. Research area is further fueled by ever-increasing demand for modern probe- drug-discovery programs synthetic...

The catalytic enantioselective assembly of spirocyclic molecules featuring a spiro quaternary carbon stereocenter is currently great interest because such privileged 3D structures are widely present in natural products that exhibit broad spectrum biological and pharmacological activities. This review summarizes the advances based on six major synthetic strategies showcases reaction mechanisms detail. advantages limitations each strategy presented, remaining opportunities outlined.

A highly enantioselective Strecker reaction of difluoromethyl and trifluoromethyl ketoimines was developed. Remarkable fluorine effect on the reactivity selectivity is observed discussed.

A newly developed cinchonidine-derived phosphoramide 6b, simple and easily available, was identified as a powerful catalyst for the highly enantioselective Michael addition of both unprotected 3-aryl 3-alkyloxindoles to β-substituted nitroalkenes furnish C3 quaternary stereogenic carbon center with an adjacent tertiary stereocenter in up 21 : 1 diastereoselectivity 99% enantioselectivity.

We report a highly enantioselective Cu(I)-catalyzed azide-alkyne cycloaddition via asymmetric desymmetrization of oxindole-based 1,6-heptadiynes, which furnishes quaternary oxindoles bearing 1,2,3-triazole-containing moiety with 84-98% ee.

Quinidine derivative (QD)2PYR was found to catalyze the asymmetric direct amination of unprotected prochiral 3-oxindole with DIAD construct quaternary stereocenters at C3 position excellent enantioselectivity.

Abstract A rare example of a one‐pot process that involves asymmetric triple relay catalysis is reported. The key step an [1,5] electrocyclic reaction functionalized ketimines. substrates for this were obtained in situ two‐step involved the hydrogenation nitroarenes with Pd/C catalyst to yield aryl amines and their subsequent coupling isatin derivatives Brønsted acid catalyzed ketimine formation reaction. electrocyclization was by bifunctional chiral base/hydrogen bond donor catalyst. gave...

Sulfur-containing tetrasubstituted carbon stereocenters are widely present in natural products, drugs, and biologically active compounds. Catalytic enantioselective construction of such fully substituted is a current research interest, with four major synthetic strategies being developed. This review summarizes the advances this field, discusses detail advantages limitation each strategy, outlines opportunities still open for development.

Waste not want not: Reported is a strategy to improve the atom economy of Wittig reaction by using it in tandem reactions that directly employ waste Ph3PO as an in-situ-generated Lewis base catalyst/co-catalyst next step (see scheme).

Phosphoranes 2 are identified as a class of effective Lewis bases to activate chiral (salen)AlCl complex 1 enhance its electrophilicity. Accordingly, three-component catalyst system consisting 1, phosphorane 2e, and Ph3PO is developed powerful tool for asymmetric ketone cyanosilylation. In particular, an unprecedented highly enantioselective cyanosilylation linear aliphatic ketones achieved. A tandem Wittig-cyanosilylation sequence starting from 2a enals 10 further achieved, which internally...

A γ-carboxylation of α-CF₃ alkenes with CO₂ using platinum plate as both working cathode and nonsacrificial anode has been developed.

It is reported for the first time that Hg(II) can catalyze cyclopropanation of diazo reagents and alkenes, which contributes to unprecedented highly diastereo- enantioselective synthesis spirocyclopropyloxindoles.

The catalytic asymmetric electrophilic amination has been established as a fruitful methodology for the construction of nitrogen-bearing tetrasubstituted carbon stereocenters, with its roots nourished by latest achievements in chiral catalysis and synthetic strategies. This review summarizes recent progresses, briefly discusses reaction mechanism challenges this context, outlines opportunities future development. 1 Introduction 2 Transformations Based on Azodicarboxylates 2.1 α-Substituted...

Recent progress in asymmetric catalysis using chiral only-at-metal complexes is reviewed, with emphasis on Ir(<sc>iii</sc>) and Rh(<sc>iii</sc>) systems.

Highly enantioselective CuAAC reactions for the synthesis of versatile <italic>P</italic>-chiral phosphorus synthons featuring a ethynyl group were developed.

We report the first highly selective kinetic resolution of racemic α-chiral azides via Cu-catalyzed azide-alkyne cycloaddition (CuAAC). Newly developed pyridine-bisoxazoline (PYBOX) ligands, bearing a C4 sulfonyl group, enable effective derived from privileged scaffolds such as indanone, cyclopentenone, and oxindole, their asymmetric CuAAC to afford α-tertiary 1,2,3-triazoles with high excellent ee values. DFT calculations control experiments reveal that group decreases Lewis basicity ligand...

The direct α-cyanoamination of isatins using TMSCN has been developed, which is carried out in methanol without any catalyst. A new bifunctional cinchona alkaloid-based phosphinamide catalyst 7 could promote the Strecker reaction derived ketimine with up to 74% ee.

Au-dacious ring synthesis: An efficient synthesis of the A–D rings azaspiracid has been developed by using a Co-catalyzed oxaetherification to form fused 2,5-trans-configured trisubstituted tetrahydrofuran D ring, and an unprecedented Au-catalyzed bis-spiroketal formation wherein bridging alkyne served as surrogate for C10 ketal (see scheme; PMB=para-methoxybenzyl, TBDPS=tert-butyldiphenylsilyl).

We report a tandem asymmetric aldehyde–alkyne–amine (A3) coupling-carboxylative cyclization sequence for the highly enantioselective synthesis of chiral N-aryl 2-oxazolidinones. This is rare example multicatalyst-promoted reaction using CO2 as C1 synthon. Notably, copper species and ligand from upstream A3 are internally reused to facilitate downstream silver-catalyzed carboxylative cyclization.

We report the first organocatalytic asymmetric synthesis of 3,3-disubstituted oxindoles featuring two heteroatoms at C3 position. Importantly, 3-thiooxindoles and 3-alkoxyoxindoles are demonstrated to be reactive nucleophiles for development catalytic reactions time.