The asymmetric arylation of 2,2-dialkyl cyclopent-4-ene-1,3-diones with aryl boronic acids was found to be efficiently catalyzed by a chiral diene–rhodium μ-chloro dimer, [{RhCl((R)-diene*)}₂], in the absence of bases in toluene/H₂O to give 2,2-dialkyl 4-aryl cyclopentane-1,3-diones in high yields with high enantioselectivity. Such compounds can not be obtained with high enantiomeric purity under the standard basic conditions used for rhodium-catalyzed asymmetric arylation because the α-aryl ketone products undergo racemization under the basic conditions.

The asymmetric arylation of 2,2-dialkyl cyclopent-4-ene-1,3-diones with aryl boronic acids was found to be efficiently catalyzed by a chiral diene–rhodium μ-chloro dimer, [{RhCl((R)-diene*)}₂], in the absence of bases in toluene/H₂O to give 2,2-dialkyl 4-aryl cyclopentane-1,3-diones in high yields with high enantioselectivity. Such compounds can not be obtained with high enantiomeric purity under the standard basic conditions used for rhodium-catalyzed asymmetric arylation because the α-aryl ketone products undergo racemization under the basic conditions.

Highly enantioselective Michael addition of 2-fluoro-1,3 diketones to nitroalkenes was developed, and the desired adducts were obtained in good chemical yields with moderate to good diastereoselectivties and excellent enantioselectivities. Subsequent stereoselective reduction of the carbonyl groups led to the preparation of a functionalized fluoroisostere of glycerol that contains four continuous stereogenic centers.

Fluorinated phosphonates are excellent surrogates of phosphates, outperforming the latter in terms of hydrolytic stability in biological systems while retaining similar activities. However, methods for preparing chiral fluorinated phosphonates are very limited. In this report, racemic α-fluoro-β-ketophosphonates were used in stereoselective Michael addition to nitroalkenes promoted by trifunctional thiourea organocatalyst. Highly functionalised α-fluoro-β-keto-γ-nitrophosphonates were obtained in high yields of 84–99% with excellent stereochemical control (96–99% ee and 3:1–34:1 d.r.).

The first phosphine-catalyzed enantioselective γ-addition with prochiral nucleophiles and 2,3-butadienoates as the reaction partners has been developed. Both 3-alkyl- and 3-aryl-substituted oxindoles could be employed in this process, which is catalyzed by a chiral phosphine that is derived from an amino acid, thus affording oxindoles that bear an all-carbon quaternary center at the 3-position in high yields and excellent enantioselectivity. The synthetic value of these γ-addition products was demonstrated by the formal total synthesis of two natural products and by the preparation of biologically relevant molecules and structural scaffolds.

A cationic palladium complex with a chiral phosphine-oxazoline ligand (iPr-phox) showed high catalytic activity and enantioselectivity in the asymmetric addition of arylboronic acids to six-membered cyclic N-sulfonyl ketimines to give high yields of the corresponding chiral cyclic sulfamidates with 96–99.9 % ee. The products have tetrasubstituted stereogenic centers with an amino group and a triaryl or alkyldiaryl group as substituents.

An enantioselective synthesis of spiropyrazolones from allenoate-derived MBH acetates and pyrazolones through a phosphine-mediated [4+1] annulation process has been developed. Spiropyrazolones were readily prepared in good chemical yields and good to high enantioselectivities. This is the first asymmetric example in which α-substituted allenoates were utilized as a C₄ synthon for phosphine-catalyzed [4+1] annulation.

The first phosphine-catalyzed enantioselective γ-addition with prochiral nucleophiles and 2,3-butadienoates as the reaction partners has been developed. Both 3-alkyl- and 3-aryl-substituted oxindoles could be employed in this process, which is catalyzed by a chiral phosphine that is derived from an amino acid, thus affording oxindoles that bear an all-carbon quaternary center at the 3-position in high yields and excellent enantioselectivity. The synthetic value of these γ-addition products was demonstrated by the formal total synthesis of two natural products and by the preparation of biologically relevant molecules and structural scaffolds.

An enantioselective synthesis of spiropyrazolones from allenoate-derived MBH acetates and pyrazolones through a phosphine-mediated [4+1] annulation process has been developed. Spiropyrazolones were readily prepared in good chemical yields and good to high enantioselectivities. This is the first asymmetric example in which α-substituted allenoates were utilized as a C₄ synthon for phosphine-catalyzed [4+1] annulation.

A cationic palladium complex with a chiral phosphine-oxazoline ligand (iPr-phox) showed high catalytic activity and enantioselectivity in the asymmetric addition of arylboronic acids to six-membered cyclic N-sulfonyl ketimines to give high yields of the corresponding chiral cyclic sulfamidates with 96–99.9 % ee. The products have tetrasubstituted stereogenic centers with an amino group and a triaryl or alkyldiaryl group as substituents.

Tryptophan-derived tertiary amine-thiourea catalysts were shown to promote a cascade oxa-Michael–Michael reaction between ethylene β-keto esters and nitroolefins, resulting in the formation of 3,3-disubstituted 4-chromanones bearing a quaternary center in high diastereoselectivity and enantioselectivity. The chromanone products can be readily converted to biologically important fused and spiro tricyclic chromans.

Novel Cinchona alkaloid-derived guanidines catalyze stereoselective aminations of fluorinated keto esters, affording products with fluorine-containing quaternary stereogenic centers in excellent yields and with moderate to high enantioselectivities.