We disclose herein a highly enantioselective de novo-synthesis of chiral 1-cyclopentenyl-α-keto esters starting from a simple bis-silyl-1,3-dienediolate and α,β-unsaturated aldehydes via a domino vinylogous Michael-intramolecular Knoevenagel-type condensation. The cyclopentenes proved to be highly versatile and were readily converted into various structural motifs.

Novel guanidine-bisurea bifunctional organocatalysts 5 bearing a chiral pyrrolidine moiety on guanidine were designed with the guidance of DFT calculations. The resulting organocatalysts 5 were examined for α-hydroxylation of tetralone-derived β-keto esters, and good selectivity was obtained with 5j bearing a methoxymethyl ether-containing chiral pyrrolidine moiety.

Highly efficient asymmetric aldol reactions between α,β-unsaturated keto esters and acyclic ketones catalyzed by chiral diamines are reported. The corresponding products were obtained in excellent yields with excellent enantioselectivities. The absolute configuration for the product was determined by X-ray analysis. A variety of substrates were tolerable in the present catalytic system.

β-keto esters are used as precursors for the synthesis of β-amino acids, which are building blocks for some classes of pharmaceuticals. Here we describe the comparison of screening procedures for hydrolases to be used for the hydrolysis of β-keto esters, the first step in the preparation of β-amino acids. Two of the tested high throughput screening (HTS) assays depend on coupled enzymatic react...