Chiral bisphosphine Ph-BPE ligand: a rising star in asymmetric synthesis

Chemical Society Reviews, Год журнала: 2024, Номер 53(13), С. 6735 - 6778

Опубликована: Янв. 1, 2024

The review summarizes the increasing applications of chiral bisphosphine ligand Ph-BPE in catalytic asymmetric reactions past twenty years.

Язык: Английский

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Nickel-catalyzed asymmetric hydrogenation for the preparation of α-substituted propionic acids

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Июнь 28, 2024

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 )-dihydroartemisinic acid 99.8:0.2 dr (diastereomeric ratio) 5000 S/C, which essential intermediate antimalarial drug Artemisinin. The reaction mechanism has been investigated via experiments DFT (Density Functional Theory) calculations, indicate that protonolysis C-Ni bond key intramolecular proton transfer from carboxylic group substrate, rate-determining step.

Язык: Английский

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Earth‐Abundant Nickel‐Catalyzed Asymmetric Hydrogenation^†

Chinese Journal of Chemistry, Год журнала: 2024, Номер 42(23), С. 3135 - 3156

Опубликована: Авг. 13, 2024

Comprehensive Summary Transition metal‐catalyzed asymmetric hydrogenation is an efficient and direct synthetic method to access chiral compounds, which features simplicity, easy working‐up process, high atomic economy. It typically relies on precious transition metal catalytic systems, including ruthenium, rhodium, iridium palladium, always face the difficulties of limited resources, cost, environmental contamination. Therefore, great efforts were made apply earth‐abundant, low (non‐)toxic, environmentally friendly metals, such as iron, cobalt, nickel copper, in past decades, some considerable breakthroughs have been obtained. In this review, we mainly summarized recent research progress nickel‐catalyzed prochiral unsaturated molecules, olefins, imines ketones. And continuous development systems application them into challenging prospected future. Key Scientists has regarded important approach molecules. The first example homogeneous was developed by Knowles Horner 1968, respectively. 1971, Kagan privileged DIOP ligand for hydrogenation. Halpern Brown deep studies Rh‐catalyzed 1977, Noyori a powerful BINAP 1980. Owing Noyori's contribution field hydrogenation, they awarded Nobel Prize Chemistry 2001. 1984, Ohkubo pioneering earth‐abundant Ni‐catalyzed ethyl α‐methylcrotonate. A many scientists tremendous ligands, as, Bosnich, Kumada, Giongo, Takaya, Miyashima, Achiwa, Burk, Pflaltz, Chan, X. Zhang, Imamoto, Zhou, Genet, Sannicolo, Ding, Hoge, W. Z. Tang, these ligands owned wide addition, Fan investigation aromatic heterocyclic compounds. importance (transfer) promoted cheap researchers, Hamada, Gao, J. S. Chirik, Y.‐G. Lv, Dong, Fu, Deng, Hou, there are other that also transformation, with too space list all them.

Язык: Английский

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Synthesis of chiral sulfones via nickel-catalyzed asymmetric hydrogenation

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(10), С. 2786 - 2792

Опубликована: Янв. 1, 2024

A Ni-catalyzed highly enantioselective hydrogenation of α,β-unsaturated sulfones was successfully realized achieving high yields (91–98%) and excellent enantioselectivities (up to 99.9% ee).

Язык: Английский

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Enantioselective Synthesis of Chiral β²-Amino Phosphorus Derivatives via Nickel-Catalyzed Asymmetric Hydrogenation

Journal of the American Chemical Society, Год журнала: 2024, Номер unknown

Опубликована: Дек. 27, 2024

Compared with chiral β3-amino phosphorus compounds, which can be easily derived from natural optically pure α-amino acids, obtaining β2-amino derivatives remains a challenge. These derivatives, cannot amino possess unique biological activities or potential catalytic activities. Herein, highly enantioselective hydrogenation for the preparation of E-β-enamido compounds is reported by using green and low-cost earth-abundant metal nickel catalyst (13 examples 99% ee). In particular, this system provides same enantiomer product E- Z-alkene substrates, E/Z-substrate mixtures provide good results (up to 96% The products diversely derivatized, exhibit as novel β2-aminophosphine ligands. Density functional theory calculations reveal that weak attractive interactions between substrate are crucial achieving perfect enantioselectivities. addition, different coordination modes Z-substrates may result in formation product.

Язык: Английский

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A dicationic nickel complex-catalyzed asymmetric synthesis of chiral benzylic amines: evolution from reductive amination to borrowing hydrogen reaction

Chinese Chemical Letters, Год журнала: 2025, Номер unknown, С. 111148 - 111148

Опубликована: Март 1, 2025

Язык: Английский

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Stereoselective Nickel-Catalyzed Iterative 1,2-Reduction of Trisubstituted Enones to Cycloalkanols Bearing Two Contiguous Stereocenters

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Апрель 14, 2025

Herein we first report a nickel-catalyzed asymmetric iterative 1,2-reduction of trisubstituted enones to cycloalkanols with two contiguous stereocenters in high yields excellent diastereo- and enantioselectivities (36 examples, up 98.5:1.5 er, >20:1 dr, TON = 500). The combined experimental computational mechanistic studies suggested energy changes during consecutive reduction processes provided range unique rationales that have not been disclosed hydrogenation-related studies.

Язык: Английский

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Highly enantioselective synthesis of both enantiomers of tetrahydroquinoxaline derivatives via Ir-catalyzed asymmetric hydrogenation

Chemical Science, Год журнала: 2024, Номер 15(37), С. 15243 - 15254

Опубликована: Янв. 1, 2024

A novel solvent-controlled asymmetric hydrogenation protocol was developed. Both enantiomers of chiral THQs were efficiently synthesised with excellent enantioselectivities. Mechanistic studies reveal the origin enantioselectivity.

Язык: Английский

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Nickel-Catalyzed Chemo- and Enantioselective Hydrogenation and Deuteration of α,β-Unsaturated Ketimines Using Alcohols: Synthesis of Deuterated Chiral Allylic Amines

Organic Letters, Год журнала: 2023, Номер 25(48), С. 8739 - 8744

Опубликована: Ноя. 28, 2023

A nickel-catalyzed chemoselective asymmetric transfer hydrogenation of α,β-unsaturated ketimines using ethanol as a hydrogen donor under mild conditions that avoid high-pressure gas was developed. With this catalyst, C1-selective deuterated chiral allylic amines were efficiently synthesized only stoichiometric 2-propanol-d8. Mechanism studies demonstrated the formation nickel hydride intermediate.

Язык: Английский

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Nickel-catalyzed enantioselective reductive amination of benzylic ketones in alcohols

Science China Chemistry, Год журнала: 2024, Номер 67(8), С. 2566 - 2570

Опубликована: Июнь 27, 2024

Язык: Английский

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