A highly selective multicomponent carbonyl allylation reaction of 1,3-butadienes, aryldiazonium tetrafluoroborates, and aldehydes has been established under the combined catalysis of palladium acetate and chiral anion phase transfer to render the favorable assembly of chiral Z-configured homoallylic alcohols in high yields and with excellent levels of enantioselectivity.

A highly selective multicomponent carbonyl allylation reaction of 1,3-butadienes, aryldiazonium tetrafluoroborates, and aldehydes has been established under the combined catalysis of palladium acetate and chiral anion phase transfer to render the favorable assembly of chiral Z-configured homoallylic alcohols in high yields and with excellent levels of enantioselectivity.

The sodium salts of anionic chiral cobalt(III) complexes (CCC⁻Na⁺) have been found to be efficient catalysts of the asymmetric Povarov reaction of easily accessible dienophiles, such as 2,3-dihydrofuran, ethyl vinyl ether, and an N-protected 2,3-dihydropyrrole, with 2-azadienes. Ring-fused tetrahydroquinolines with up to three contiguous stereogenic centers were thus obtained in high yields, excellent diastereoselectivities (endo/exo up to >20:1), and high enantioselectivities (up to 95:5 e.r.).

An unprecedented gold-catalyzed multiple cascade reaction between 2-alkynyl arylazides and alkynols has been developed, allowing for the step-economical synthesis of pyrroloindolone derivatives with a wide range of structural diversity. In this reaction, the gold complex participates in triple catalysis in tandem fashion. Moreover, the efficient chirality transfer from optically pure alkynol substrates enables facile access to chiral pyrroloindolone derivatives with two stereogenic centers, including a quaternary one, with excellent levels of optical purity.

A highly enantioselective organocatalytic substitution of 3-(1-tosylalkyl)indoles with oxindoles has been established by using chiral bifunctional organocatalysts, providing an efficient entry to multiply functionalized 3,3′-disubstituted oxindoles, and was exploited as the key step to enable the first asymmetric total synthesis of optically pure (+)-trigolutes B to be accomplished in a concise manner, within seven steps with an 18 % overall yield.

The first enantioselective dearomatizative spirocyclization of 1-hydroxy-N-aryl-2-naphthamide derivatives has been accomplished by chiral organoiodine catalysis to stereoselectively create an all-carbon stereogenic center, providing a straightforward approach to access spirooxindole derivatives in good yields and with high to excellent levels of enantioselectivity. Chiral hypervalent phenyl-λ³-iodanes generated in situ from the oxidation of the chiral phenyl iodine actually participate in the asymmetric oxidative dearomatizative spirocyclization reaction.

The sodium salts of anionic chiral cobalt(III) complexes (CCC⁻Na⁺) have been found to be efficient catalysts of the asymmetric Povarov reaction of easily accessible dienophiles, such as 2,3-dihydrofuran, ethyl vinyl ether, and an N-protected 2,3-dihydropyrrole, with 2-azadienes. Ring-fused tetrahydroquinolines with up to three contiguous stereogenic centers were thus obtained in high yields, excellent diastereoselectivities (endo/exo up to >20:1), and high enantioselectivities (up to 95:5 e.r.).

A chiral phase-transfer catalyst, derived from the combination of cinchona alkaloid backbone and BINOL skeleton, enabled a Mannich reaction of glycine Schiff base with N-Boc-imines to generate α,β-diamino acid derivatives in excellent yields (up to 99%) and with high diastereo- and enantioselectivities (up to>20:1 dr, 96% ee).

An asymmetric organocatalytic direct CH/CH oxidative coupling reaction of N¹,N³-diphenylmalonamides has been well established by using chiral organoiodine compounds as catalysts, wherein four CH bonds were stereoselectively functionalized to give structurally diverse spirooxindoles with high levels of enantioselectivity. More importantly, the findings indicated that chiral hypervalent organoiodine reagents can serve as alternative catalysts for the creation of enantioselective functionalization of inactive CH bonds.

A combination of either ruthenium(II) or rhodium(II) complexes and quinine-derived squaramide enables 3-diazooxindoles, indoles, and nitroalkenes to undergo highly efficient asymmetric three-component reactions, thus affording optically active 3,3′-bis(indole)s through a consecutive CC bond-forming sequence, which turned out to be applicable to the facile total synthesis of (−)-folicanthine.

The first enantioselective α-allylation of aldehydes with terminal alkenes has been realized by combining asymmetric counteranion catalysis and palladium-catalyzed allylic CH activation. This method can tolerate a wide scope of α-branched aromatic aldehydes and terminal alkenes, thus affording allylation products in high yields and with good to excellent levels of enantioselectivity. Importantly, the findings suggest a new strategy for the future creation of enantioselective CH/CH coupling reactions.

An asymmetric organocatalytic direct CH/CH oxidative coupling reaction of N¹,N³-diphenylmalonamides has been well established by using chiral organoiodine compounds as catalysts, wherein four CH bonds were stereoselectively functionalized to give structurally diverse spirooxindoles with high levels of enantioselectivity. More importantly, the findings indicated that chiral hypervalent organoiodine reagents can serve as alternative catalysts for the creation of enantioselective functionalization of inactive CH bonds.

A combination of either ruthenium(II) or rhodium(II) complexes and quinine-derived squaramide enables 3-diazooxindoles, indoles, and nitroalkenes to undergo highly efficient asymmetric three-component reactions, thus affording optically active 3,3′-bis(indole)s through a consecutive CC bond-forming sequence, which turned out to be applicable to the facile total synthesis of (−)-folicanthine.

The first enantioselective α-allylation of aldehydes with terminal alkenes has been realized by combining asymmetric counteranion catalysis and palladium-catalyzed allylic CH activation. This method can tolerate a wide scope of α-branched aromatic aldehydes and terminal alkenes, thus affording allylation products in high yields and with good to excellent levels of enantioselectivity. Importantly, the findings suggest a new strategy for the future creation of enantioselective CH/CH coupling reactions.

The combination of relay and cooperative catalysis with a gold/palladium/Brønsted acid ternary system renders a cascade hydroamination/allylic alkylation reaction to provide an unprecedented entry to pyrrolidine derivatives in high yields.

Catalytic asymmetric construction of the biologically important spiro[pyrrolidin-3,2′-oxindole] scaffold with contiguous quaternary stereogenic centers in excellent stereoselectivities (up to >99:1 d.r., 98 % ee) has been established by using an organocatalytic 1,3-dipolar cycloaddition of isatin-based azomethine ylides. This protocol represents the first example of catalytic asymmetric 1,3-dipolar cycloadditions involving azomethine ylides generated in situ from unsymmetrical cyclic ketones. In addition, theoretical calculations were performed on the transition state of the reaction to understand the stereochemistry. Preliminary bioassays with these spiro[pyrrolidin-3,2′-oxindole] revealed that several compounds showed moderate cytotoxicity to SW116 cells.

An asymmetric Darzens reaction of aldehydes with diazo-N,N-dimethylacetamide (3) catalyzd by an air-stable and storable chiral zirconium Lewis acid catalyst, which is formed from 3,3′-diiodobinaphthol and tetrabutoxyzirconium, gives solely the cis-glycidic amides in high yields with excellent enantioselectivity (up to 97% yield, >99% ee).

An on-water, asymmetric, and direct syn-aldol reaction of aliphatic ketones with aromatic aldehydes catalyzed by a primary amino acid-based organocatalyst afforded the syn-aldol adducts in high yields with excellent diastereo- and enantioselectivities (up to > 20/1 dr, >99% ee), and a highly enantioselective syn-aldol reaction of dihydroxyacetone with a variety of aldehydes in THF proceeded with 14/1 to >20/1 dr and 92 to >99% ee. Water not only accelerated the reaction, but also enhanced the enantioselectivity. This positive water effect might arise from the hydrogen bond formed between a pendant hydroxy group of surface water molecules at the hydrophobic interface with the amide oxygen of the organocatalyst, which increases the acidity of the amide NH and thereby strengthens the related hydrogen bond formed with the aldehyde.

An organocatalytic asymmetric formal [3+3] cycloaddition reaction of α,β-unsaturated aldehydes with Nazarov reagents promoted by prolinol derivatives afforded, after oxidation, 3,4-dihydropyranones in good yields with high enantioselectivities of up to 97% ee.