Abstract An efficient nickel‐catalyzed asymmetric hydrogenation of N ‐ t Bu sulfonyl imines was developed with excellent yields and enantioselectivities using ( R , )‐QuinoxP* as a chiral ligand. The use much lower catalyst loading (0.0095 mol %, S/C=10500) represents the highest catalytic activity for Ni‐catalyzed hydrogenations reported so far. Mechanistic studies suggest that coordination equilibrium exists between nickel salt its complex, excess promotes formation active Ni‐complex,...

Abstract Chiral α-aryl glycines play a key role in the preparation of some bioactive products, however, their catalytic asymmetric synthesis is far from being satisfactory. Herein, we report an efficient nickel-catalyzed hydrogenation N -aryl imino esters, affording chiral high yields and enantioselectivities (up to 98% ee). The can be conducted on gram scale with substrate/catalyst ratio up 2000. obtained - p -methoxyphenyl glycine derivatives are not only directly useful secondary amino...

Earth-abundant nickel, coordinated with a suitable chiral bisphosphine ligand, was found to be an efficient catalyst for the asymmetric hydrogenation of 2-amidoacrylates, affording α-amino acid esters in quantitative yields and excellent enantioselectivity (up 96 % ee). The active component studied by NMR HRMS, which helped us realize high catalytic efficiency on gram scale low loading (S/C=2000). hydrogenated products could simply converted into acids, β-amino alcohols, their bioactive...

The catalytic asymmetric synthesis of the anti-COVID-19 drug Remdesivir has been realized by coupling P-racemic phosphoryl chloride with protected nucleoside GS441524. chiral bicyclic imidazole catalyst used is crucial for dynamic kinetic transformation (DyKAT) to proceed smoothly high reactivity and excellent stereoselectivity (96 % conv., 22:1 SP:RP). Mechanistic studies showed that this DyKAT a first-order visual reaction dependent on concentration. unique skeleton carbamate substituent...

Asymmetric hydrogenation of sterically hindered substrates still constitutes a long-standing challenge in the area asymmetric catalysis. Herein, an efficient palladium acetate (an inexpensive Pd salt with low toxicity) catalyzed N-tosylimines is realized high catalytic activities (S/C up to 5000) and excellent enantioselectivities (ee 99.9%). Quantum chemical calculations suggest that uniformly are observed due structurally different S- R-reaction pathways.

First hand: The first example of a palladium-catalyzed asymmetric hydrogenation α-acyloxy ketones (1) was accomplished to give the hydrogenated products 2 with by far highest catalytic efficiency in up quantitative conversions and excellent enantioselectivities. could serve as important intermediates for preparation many drug candidates. TFE=2,2,2-trifluoroethanol.

Chiral α-substituted ethylphosphonate and ethylphosphine oxide compounds are widely used in drugs, pesticides, ligands. However, their catalytic asymmetric synthesis is still rare. Of the only hydrogenation methods available at present, all cases use rare metal catalysts. Herein, we report an efficient earth-abundant transition-metal nickel catalyzed affording corresponding chiral products with up to 99 % yield, 96 ee (enantiomeric excess) (99 ee, after recrystallization) 1000 S/C...

A highly chemoselective earth-abundant transition metal copper catalyzed asymmetric hydrogenation of C=O bonds exocyclic α,β-unsaturated pentanones was realized using H2 . The desired products were obtained with up to 99 % yield and 96 ee (enantiomeric excess) (99 ee, after recrystallization). corresponding chiral allylic pentanol can be converted into several bioactive molecules. mechanism investigated via deuterium-labelling experiments control experiments, which indicate that the...

Catalyzed by a rhodium complex of P-stereogenic diphosphine ligand (R)-2-tert-butylmethylphosphino-3-(di-tert-butylphosphino)quinoxaline ((R)-3H-QuinoxP*), five-membered cyclic α-dehydroamino ketones bearing endocyclic vinyl and keto-carbonyl groups were sequentially hydrogenated to give chiral trans-β-amino alcohols with two contiguous stereocenters in quantitative conversions, excellent enantioselectivities good diastereoselectivities.

The asymmetric allylation of glycine iminoesters has been accomplished through a synergistic Pd/Cu catalyst system, affording range α-substituted α-amino acids in high yields and with excellent enantioselectivities (88 → 99% ee). introduction Cu-P,N-metallocenyl complex-activated iminoester to the chiral palladium-catalyzed allylic process is crucial owing its reactivity enantioselectivities. Importantly, this dual catalysis strategy can be used for alkylation prochiral amide derivatives,...

Abstract An efficient nickel‐catalyzed asymmetric hydrogenation of hydrazones to chiral hydrazines has been realized with up 99 % yield and 99.4 : 0.6 er. Deuterium labelling experiments indicated that the hydrazone substrates undergo imine‐enamine tautomerization in mixed solvents. Studies on effects acids revealed required acid assistance promoted dissociation active nickel catalyst catalytic cycle.

Abstract Transition metal-catalyzed asymmetric hydrogenation is one of the most efficient methods for preparation chiral α-substituted propionic acids. However, research on this method, employing cleaner earth-abundant metal catalysts, still insufficient in both academic and industrial contexts. Herein, we report an nickel-catalyzed acrylic acids affording corresponding with up to 99.4% ee (enantiomeric excess) 10,000 S/C (substrate/catalyst). In particular, method can be used obtain ( R...

Weak attractive non‐covalent interactions, specifically CH/π⋯HC/π and CH⋯O/N contacts, between catalysts substrates have recently gained renewed attention in asymmetric hydrogenations, despite their historical underappreciation due to challenges detection. Emerging evidence underscores the significant role of these interactions improving reactivity and/or enantioselectivity, particularly sustainable catalytic systems that utilize Earth‐abundant transition metals. This minireview summarizes...

A chemoselective C-O bond cleavage of the ester alkyl side-chain α-acyloxy ketones was realized for first time by a highly efficient palladium-catalyzed hydrogenolysis (S/C=6000, highest catalytic efficiency far). Furthermore, kinetic resolution developed enantioselective with good yields and up to 99 % ee.

β-Branched simple enamides were hydrogenated to give β-stereogenic amines in quantitative yields and with excellent enantioselectivities.

Abstract An efficient nickel‐catalyzed asymmetric hydrogenation of N ‐ t Bu sulfonyl imines was developed with excellent yields and enantioselectivities using ( R , )‐QuinoxP* as a chiral ligand. The use much lower catalyst loading (0.0095 mol %, S/C=10500) represents the highest catalytic activity for Ni‐catalyzed hydrogenations reported so far. Mechanistic studies suggest that coordination equilibrium exists between nickel salt its complex, excess promotes formation active Ni‐complex,...

Chiral C-X (X＝N, O, P, B, F, etc.) bond fragments are present in a wide variety of natural and pharmaceutically active molecules.Transition metal-catalyzed asymmetric hydrogenation is one the most attractive strategies for synthesis these chiral compounds.Among many transition metal catalysts, earth-abundant metals (iron, cobalt, nickel, copper) have been used to replace rare (rhodium, ruthenium, iridium palladium) due their abundant reserves, low toxicity, environmental friendliness.At...

Catalyzed by a rhodium complex of P-stereogenic diphosphine trichickenfootphos, five-membered cyclic α-dehydroamino ketones bearing endocyclic acyl and vinyl groups were hydrogenated to give chiral α-amino with quantitative conversions excellent enantioselectivities.

An efficient Pd(<sc>ii</sc>)-catalyzed aerobic intermolecular 1,2-difunctionalization of conjugated dienes was developed for the synthesis functionalized morpholines and 2-morpholones.

An efficient Pd(OAc)2-catalyzed asymmetric hydrogenation of α-iminoesters was realized for the first time at 1 atm hydrogen pressure and room temperature. Pd(OAc)2, a less expensive Pd salt with low toxicity, found to be most suitable catalyst precursor rather than Pd(TFA)2 which is usually choice homogeneous hydrogenation. The chiral α-arylglycine fragments are widely in many products bioactive molecules.

A Co(<sc>ii</sc>)/BOX-catalyzed asymmetric allylation of spiroepoxyoxindoles was developed, which is the first stereoconvergent epoxides, yielding chiral oxindoles bearing quaternary stereocenters.

Abstract Earth‐abundant nickel, coordinated with a suitable chiral bisphosphine ligand, was found to be an efficient catalyst for the asymmetric hydrogenation of 2‐amidoacrylates, affording α‐amino acid esters in quantitative yields and excellent enantioselectivity (up 96 % ee ). The active component studied by NMR HRMS, which helped us realize high catalytic efficiency on gram scale low loading (S/C=2000). hydrogenated products could simply converted into acids, β‐amino alcohols, their...