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The development of sustainable, functional-group-tolerant catalysis is highly significant from the perspectives of safety, user-friendliness, and cost-effectiveness. We report herein the triple hydrogen-bonding donor activator N -triflyl phosphoric triamide (N -TPT ) for the synergistic Brønsted acid aquacatalysis of multicomponent allylation 'on-water'. The reaction demonstrated remarkable efficiency in converting polar diol substrate, such as 1,3-dihydroxyacetone, into α-tertiary amine derivative incorporating homoallylic amine functionalities using bulk water as the reaction medium. The single crystal X-ray structure and control experiments highlighted the crucial role of multiple hydrogen bonds in enabling this aqueous reaction. [ABSTRACT FROM AUTHOR]

A palladium/chiral N,N′-disulfonyl bisimidazoline (Bim)-catalyzed asymmetric addition of arylboronic acids to isoquinoline-1,3,4-trione-derived ketimines is reported, leading to the generation of a series of functionalized isoquinoline-1,3(2H,4H)-diones bearing one quaternary carbon-amino functionality in good to excellent yields with ≥95% ee in most cases. The reaction has remarkable compatibility with both substrate scopes, providing a highly enantioselective entry to chiral heterocyclic α-tertiary amines.

Arylation of ketimines is the most straightforward strategy for constructing chiral α‐tertiary amines, important structural motifs found in natural products and biologically active compounds. This comprehensive review highlights the achievements in the transition metal‐catalyzed and organocatalyzed asymmetric arylations of ketimines from the seminal report published in 2010 till November 2023. The review is divided into three chapters: (1) Arylation of diaryl ketimines, (2) Arylation of aryl‐alkyl and aryl‐acyl ketimines, and (3) Arylation of acyl‐alkyl and dialkyl ketimines. Each chapter is further divided into transition metal‐catalyzed reactions (grouped by individual metals) and organocatalyzed reactions. The covered literature includes emphasis on the advantages of the reported methodology, its scope and limitations, and the description of the transition state (where applicable). [ABSTRACT FROM AUTHOR]

A new, straightforward, highly efficient, and mild catalytic protocol for the synthesis of α‐tertiary propargylamines, via the multicomponent KA2 reaction (Ketone‐Amine‐Alkyne), employing well‐defined, sustainable copper(I) complexes bearing N‐heterocyclic carbene ligands, is reported herein. The methodology uses very low catalyst loading under moderate heating to achieve the construction of a wide range of propargylamines in good to excellent yields in very short reaction times. Challenging substrates, including acyclic linear ketones, aromatic ketones, and electron‐poor aromatic alkynes, as well as substrates bearing synthetically valuable functionalities, are well tolerated. [ABSTRACT FROM AUTHOR]

A commercially available cobalt complex Cp*CoIII(CO)I2 has been found to effectively catalyze the diamination of α‐alkyl styrenes with anilines under a mild reaction condition, using dioxygen as the oxidant. This reaction features a reasonably good substrate scope of amines and a good functional group tolerance. Preliminary mechanistic studies have shown that Cp*CoIII(CO)I2 alone can promote the diamination reaction. [ABSTRACT FROM AUTHOR]

Enantioselective construction methods of chiral derivatives of α-tertiary amines using acyclic and cyclic trifluoromethylketimines are considered. The importance of a trifluoromethyl group in the structure of ketimine substrates for effective asymmetric addition of C-nucleophilic reagents in the presence of metal complex catalysts or organocatalysts is emphasized. The practical application of these chiral products in medicinal chemistry is covered. [ABSTRACT FROM AUTHOR]

A copper‐catalyzed enantioselective transformation of tris(hydroxymethyl)aminomethane‐derived aminotriols was developed to provide multisubstituted oxazolines with a tetrasubstituted carbon center. The present transformation consisted of sequential reactions involving mono‐sulfonylation of aminotriols, subsequent intramolecular cyclization to afford prochiral oxazoline diols, and sulfonylative asymmetric desymmetrization of resultant oxazoline diols. In addition, the kinetic resolution process would be involved in the sulfonylative asymmetric desymmetrization step, which would amplify the enantiopurities of the desired products. Various aminotriols were tolerated in the present reaction, affording the desired oxazolines in good to high yields with excellent enantioselectivities. The synthetic utility of the present reaction was demonstrated by the transformation of the optically active oxazoline into a chiral α‐tertiary amine motif.Trying triols: A copper‐catalyzed enantioselective transformation of N‐acyl aminotriols with arylsufonyl chlorides is developed to access optically active 4,4‐disubstituted oxazolines under mild reaction conditions. The present reaction involves a Cu‐catalyzed mono‐sulfonylation, intramolecular cyclization to provide prochiral oxazoline diols, and a Cu‐catalyzed sulfonylative asymmetric desymmetrization of oxazoline diols. [ABSTRACT FROM AUTHOR]

A copper-catalyzed enantioselective transformation of tris(hydroxymethyl)aminomethane-derived aminotriols was developed to provide multisubstituted oxazolines with a tetrasubstituted carbon center. The present transformation consisted of sequential reactions involving mono-sulfonylation of aminotriols, subsequent intramolecular cyclization to afford prochiral oxazoline diols, and sulfonylative asymmetric desymmetrization of resultant oxazoline diols. In addition, the kinetic resolution process would be involved in the sulfonylative asymmetric desymmetrization step, which would amplify the enantiopurities of the desired products. Various aminotriols were tolerated in the present reaction, affording the desired oxazolines in good to high yields with excellent enantioselectivities. The synthetic utility of the present reaction was demonstrated by the transformation of the optically active oxazoline into a chiral α-tertiary amine motif. [ABSTRACT FROM AUTHOR]

[Display omitted] Methods of copper-catalyzed alkylation of indoles and anilines with tertiary alkyl bromides were reported. These protocols provided various N - tert -alkyl 3-substituted indoles and electron-deficient N - tert -alkyl anilines in moderate to good yields via C N coupling. [ABSTRACT FROM AUTHOR]

We demonstrated a ruthenium-catalyzed regioselective allylic amination of tertiary allylic esters with various amines using [Cp*Ru(CH3CN)3][PF6]/5,5'-dimethyl-2,2'-bipyridine (5,5'-diMe-2,2'-bpy) and related ruthenium catalytic systems, and successfully obtained a diverse range of α-tertiary amines as single regioisomers. The present ruthenium catalytic system was effective for reactions with various types of amines. [ABSTRACT FROM AUTHOR]