Catalytic Alkyne Arylation Using Amines as Traceless Directing Groups

By developing a Pd(0)/Mandyphos catalyst, we have achieved a three-component aminoarylation of alkynes to generate enamines, which upon hydrolysis yield either <i>α</i>-arylphenones or <i>α</i>,<i>α</i>-diarylketones. This Pd-catalyzed method overcomes well-established pathways to enable the use of amines as traceless directing groups for C–C bond formation

Enhanced Rate and Selectivity by Carboxylate Salt as a Basic Cocatalyst in Chiral N‑Heterocyclic Carbene-Catalyzed Asymmetric Acylation of Secondary Alcohols

The rate and enantioselectivity of chiral NHC-catalyzed asymmetric acylation of alcohols with an adjacent H-bond donor functionality are remarkably enhanced in the presence of a carboxylate cocatalyst. The degree of the enhancement is correlated with the basicity of the carboxylate. With a cocatalyst and a newly developed electron-deficient chiral NHC, kinetic resolution and desymmetrization of cyclic diols and amino alcohols were achieved with extremely high selectivity (up to <i>s</i> = 218 and 99% ee, respectively) at a low catalyst loading (0.5 mol %). This asymmetric acylation is characterized by a unique preference for alcohols over amines, which are not converted into amides under the reaction conditions

Enhanced Rate and Selectivity by Carboxylate Salt as a Basic Cocatalyst in Chiral N‑Heterocyclic Carbene-Catalyzed Asymmetric Acylation of Secondary Alcohols

The rate and enantioselectivity of chiral NHC-catalyzed asymmetric acylation of alcohols with an adjacent H-bond donor functionality are remarkably enhanced in the presence of a carboxylate cocatalyst. The degree of the enhancement is correlated with the basicity of the carboxylate. With a cocatalyst and a newly developed electron-deficient chiral NHC, kinetic resolution and desymmetrization of cyclic diols and amino alcohols were achieved with extremely high selectivity (up to <i>s</i> = 218 and 99% ee, respectively) at a low catalyst loading (0.5 mol %). This asymmetric acylation is characterized by a unique preference for alcohols over amines, which are not converted into amides under the reaction conditions

Enhanced Rate and Selectivity by Carboxylate Salt as a Basic Cocatalyst in Chiral N‑Heterocyclic Carbene-Catalyzed Asymmetric Acylation of Secondary Alcohols

The rate and enantioselectivity of chiral NHC-catalyzed asymmetric acylation of alcohols with an adjacent H-bond donor functionality are remarkably enhanced in the presence of a carboxylate cocatalyst. The degree of the enhancement is correlated with the basicity of the carboxylate. With a cocatalyst and a newly developed electron-deficient chiral NHC, kinetic resolution and desymmetrization of cyclic diols and amino alcohols were achieved with extremely high selectivity (up to <i>s</i> = 218 and 99% ee, respectively) at a low catalyst loading (0.5 mol %). This asymmetric acylation is characterized by a unique preference for alcohols over amines, which are not converted into amides under the reaction conditions