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Even though tuning electronic effect of chiral ligands has proven to be a promising method for designing efficient catalysts, the potential to achieve highly selective reactions by this strategy remains largely unexplored. Here, we report a palladium-catalyzed enantioselective ring-closing aminoalkylative amination of aminoenynes enabled by rationally tuning the remote electronic property of 1,1'-binaphthol-derived phosphoramidites. With a tailored 6,6'-CN-substituted 1,1'-binaphthol-derived phosphoramidite as a ligand, a broad range of aromatic amines are compatible with this reaction, allowing the efficient synthesis of a series of enantioenriched exocyclic allenylamines bearing saturated N-heterocycles with up to >99% enantiomeric excess. Remarkably, a one-pot aminoalkylative amination/hydroamination process for the rapid synthesis of chiral spirodiamines promoted by this catalytic system is also established. Detailed mechanistic studies provide solid evidence to support that the remote electronic character of these chiral ligands can efficiently tuning the enantioselectivity by altering the length of the allylic C-Pd bond of the key catalytic intermediate. The potential applications of remote electronic effect in Pd-catalyzed asymmetric transformations have remained largely unexplored. Here, the authors report a Pd-catalyzed enantioselective ring-closing aminoalkylative amination of aminoenynes enabled by rationally tuning the remote electronic property of BINOL-derived phosphoramidites. [ABSTRACT FROM AUTHOR]

Amides are prevalent in pharmaceuticals, agrochemicals, and materials. Hydroaminocarbonylation of alkenes has emerged as one of the most direct and rapid approaches to amides. Nowadays, these reactions remain largely confined to using alkylamines as nitrogen sources, leading to sluggish reactions due to their strong binding ability and basicity. Here we show the application of abundantly available hydroxylamine hydrochloride (NH2OH·HCl) as a surrogate of ammonia for the relay hydroaminocarbonylation of simple alkenes in the presence of a convenient palladium catalyst system. The in situ formation of alkylamines from hydroxylamine hydrochloride by hydroaminocarbonylation reaction and Lossen rearrangement allows us to establish an efficient relay hydroaminocarbonylation. Notably, this transformation allows the catalytic formation of two C–N bonds with hydroxylamine hydrochloride as an amine source by incorporation of two molecules of alkene and avoids the use of alkylamines. [ABSTRACT FROM AUTHOR]