Organocatalyzed asymmetric aldol reactions of ketones and ß,γ-unsaturated α-ketoesters and phenylglyoxal hydrates.

Enantioselective aldol reactions of acetophenone with ß,γ-unsaturated α-ketoesters and cyclic ketones with phenylglyoxal hydrates were realized with cinchona alkaloid-derived thiourea catalysts. The corresponding aldol products were obtained in high yields and good to excellent diastereoselectivities and enantioselectivities (up to 95% ee).

Interplay of metalloligand and organic ligand to tune micropores within isostructural mixed-metal organic frameworks (M'MOFs) for their highly selective separation of chiral and achiral small molecules.

Four porous isostructural mixed-metal-organic frameworks (M'MOFs) have been synthesized and structurally characterized. The pores within these M'MOFs are systematically tuned by the interplay of both the metalloligands and organic ligands which have enabled us not only to direct their highly selective separation of chiral alcohols 1-phenylethanol (PEA), 2-butanol (BUT), and 2-pentanol (2-PEN) with the highest ee up to 82.4% but also to lead highly selective separation of achiral C(2)H(2)/C(2)H(4) separation. The potential application of these M'MOFs for the fixed bed pressure swing adsorption (PSA) separation of C(2)H(2)/C(2)H(4) has been further examined and compared by the transient breakthrough simulations in which the purity requirement of 40 ppm in the outlet gas can be readily fulfilled by the fixed bed M'MOF-4a adsorber at ambient conditions.

Organocatalytic High Enantioselective Synthesis of ß-Formyl-α-hydroxyphosphonates.

The cross aldol reaction between enolizable aldehydes and α-ketophosphonates was achieved for the first time by using 9-amino-9-deoxy-epi-quinine as the catalyst. ß-Formyl-α-hydroxyphosphonates were obtained in high to excellent enantioselectivities. The reaction works especially well with acetaldehyde, which is a tough substrate for organocatalyzed cross aldol reactions. The products were demonstrated to have anticancer activities.

Enantioselective synthesis of bicylco[3.2.1]octan-8-ones using a tandem Michael-Henry reaction.

Bicyclo[3.2.1]octan-8-ones have been prepared from a tandem Michael-Henry reaction between cyclohexane-1,2-diones and nitroalkenes using a quinine-derived thiourea as the catalyst. Although four stereogenic centers were created during the reaction, only two diastereomers were obtained in good diastereoselectivity and high enantioselectivity (92-99% ee). When 3-methylcyclohexane-1,2-dione (R(1) = Me) was used as the substrate, only the regioisomeric product of the corresponding thermodynamic enolate was obtained.

Direct Diastereo- and Enantioselective Vinylogous Michael Additions of Linear Enones.

A direct vinylogous Michael addition using linear vinylogous Michael donors has been developed. Notably, even γ-substituted Michael donors cleanly afforded γ-alkylated products in high yield and ee by this method. Moreover, control experiments revealed that, for these and related linear vinylogous Michael donors, the size of the Michael acceptor strongly influences whether α- or γ-alkylation occurs, not simply blocking effects of cocatalysts as suggested previously.

Highly enantioselective three-component direct Mannich reactions of unfunctionalized ketones catalyzed by bifunctional organocatalysts.

A highly stereoselective three-component direct Mannich reaction between aromatic aldehydes, p-toluenesulfonamide, and unfunctionalized ketones was achieved through an enolate mechanism for the first time with a bifunctional quinidine thiourea catalyst. The corresponding N-tosylated ß-aminoketones were obtained in high yields and excellent diastereo- and enantioselectivities (up to >99:1 dr and >99% ee).

Acetylphosphonate as a surrogate of acetate or acetamide in organocatalyzed enantioselective aldol reactions.

Highly enantioselective aldol reactions of acetylphosphonates and activated carbonyl compounds was realized with cinchona alkaloid derived catalysts, in which the acetylphosphonate was directly used as an enolate precursor for the first time. The aldol product obtained was converted in situ to its corresponding ester or amide through methanolysis or aminolysis. The overall process may be viewed as formal highly enantioselective acetate or acetamide aldol reactions, which are very difficult to achieve directly with organocatalytic methods.