We herein report a synergetic chiral primary amine and rhodium catalysis for asymmetric coupling of β-ketocarbonyls and alkynes. A series of β-ketocarbonyls could be applied to afford linear allylation products, bearing all-carbon quaternary centers in high regio- and enantioselectivities.

Highly enantioselective α‐arylation of simple ketones has been achieved by chiral primary amine catalyzed asymmetric retro‐Claisen cleavage of β‐diketones. This mild organocatalytic strategy enables the construction of α‐aryl tertiary carbon stereocenters in good yields and excellent enantioselectivities (up to 98 % ee) with the para‐quinone monoimines as aryl sources. Furthermore, oxidative catalytic asymmetric α‐arylation has also been realized with free p‐aminophenols.

We herein describe an asymmetric α-allylic allenylation of β-ketocarbonyls and aldehydes with 1,3-enynes. A synergistic chiral primary amine/Pd catalyst was identified to facilitate the utilization of 1,3-enynes as atom-economic and achiral allene precursors. The synergistic catalysis enables the construction of all-carbon quaternary centers-tethered allenes bearing non-adjacent 1,3-axial central stereogenic centers in high level of diastereo- and enantio-selectivity. By switching the configurations of ligands and aminocatalysts, diastereodivergence can be achieved and any of the four diastereoisomers can be accessed in high diastereo- and enantio- selectivity.

The use of alkylthio electrophiles in synthesis has remained elusive because of the lack of a suitable reagent that is practical and of excellent enantioselectivity and appropriate reactivity. In this work we introduce a novel alkylthio reagent based on the 2-mercapto-5methyl-1,3,4-thiadiazole (MMTD) fragment for direct alkylsulfenylation of ketones and aldehydes. It can be readily prepared by the oxidative coupling between thiadiazole and other alkylthio reagents and be combined with chiral primary aminocatalysis. This protocol provides facile access to diverse α-alkylthio quaternary carbon centers with good stereoselectivities.

Enantioselective oxidative construction of C(sp3)-S bond has been achieved by a chiral primary amine catalyst in the presence of tert-butyl hydroperoxide and a catalytic amount of tetrabutylammonium iodide. The distinctive...