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

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(13), P. 6735 - 6778

Published: Jan. 1, 2024

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

Language: Английский

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

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: June 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.

Language: 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, Journal Year: 2025, Volume and Issue: unknown, P. 111148 - 111148

Published: March 1, 2025

Language: Английский

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

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: April 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.

Language: Английский

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Synthesis of chiral sulfones via nickel-catalyzed asymmetric hydrogenation

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(10), P. 2786 - 2792

Published: Jan. 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).

Language: Английский

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Earth‐Abundant Nickel‐Catalyzed Asymmetric Hydrogenation^†

Chinese Journal of Chemistry, Journal Year: 2024, Volume and Issue: 42(23), P. 3135 - 3156

Published: Aug. 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.

Language: 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, Journal Year: 2023, Volume and Issue: 25(48), P. 8739 - 8744

Published: Nov. 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.

Language: Английский

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

Chemical Science, Journal Year: 2024, Volume and Issue: 15(37), P. 15243 - 15254

Published: Jan. 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.

Language: Английский

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

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 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.

Language: Английский

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Catalytic Deoxygenative Reduction of Hydrazides to Hydrazines via B(C₆F₅)₃‐Catalyzed Hydrosilylation

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 366(2), P. 309 - 315

Published: Dec. 12, 2023

Abstract The catalytic deoxygenative reduction of hydrazides to the corresponding alkyl hydrazine with PhSiH 3 via B(C 6 F 5 ) ‐catalyzed hydrosilylation is reported. This metal‐free protocol compatible various acylhydrazides and diacylhydrazides, giving rise a variety structurally diverse products in 63–95% yields. proper selection borane catalyst hydrosilane reductant essential for catalysis. Mechanistic investigations reveal that reaction involves hydrazone intermediate.

Language: Английский

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