P-Stereogenic Phosphorus Ligands in Asymmetric Catalysis

Chemical Reviews, Journal Year: 2024, Volume and Issue: 124(14), P. 8657 - 8739

Published: July 2, 2024

Chiral phosphorus ligands play a crucial role in asymmetric catalysis for the efficient synthesis of useful optically active compounds. They are largely categorized into two classes: backbone chirality and P-stereogenic ligands. Most reported belong to former class. Privileged ones such as BINAP DuPhos frequently employed wide range catalytic transformations. In contrast, latter class has remained small family many years mainly because their synthetic difficulty. The late 1990s saw emergence novel with superior enantioinduction ability Rh-catalyzed hydrogenation reactions. Since then, numerous have been synthesized used This Review summarizes thus far, including stereochemical electronic properties that afford high excellent enantioselectivities. Examples reactions use this described together applications construction key intermediates natural products therapeutic agents. literature covered dates back 1968 up until December 2023, centering on studies published later years.

Language: Английский

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Organometallic Mn(I) Complexes in Asymmetric Catalytic (Transfer) Hydrogenation and Related Transformations

ChemCatChem, Journal Year: 2024, Volume and Issue: 16(14)

Published: March 7, 2024

Abstract Direct asymmetric hydrogenation (AH) and transfer (ATH) are among the most efficient approaches to produce chiral building blocks. Recently, these types of transformations have witnessed a shift towards use molecular catalysts based on earth‐abundant transition metals due their ready availability, economic advantage, novel properties. With particular regard manganese, catalyst development has seen both efficiency substrate scope in AH ATH greatly improved, with emergence large number well‐defined Mn‐complexes employed this field. The reaction includes C=O bonds, reduction C=N bonds reductive C=C bonds. Herein, our survey area focuses catalytic activity such complexes, versatility routes convert substrates target molecules. We consider collected findings article will be helpful reader by providing an insight into ligand design, thereby aiding future development. Moreover, review is aimed at highlighting remarkable progress made last seven years manganese complexes for enantioselective reduction.

Language: Английский

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Nickel‐Catalyzed Asymmetric Hydrogenation of α‐Substituted Vinylphosphonates and Diarylvinylphosphine Oxides

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 62(6)

Published: Dec. 12, 2022

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 (substrate/catalyst); this also first study on of terminal olefins using a catalyst under hydrogen atmosphere. The mechanism was investigated via deuterium-labelling experiments calculations which indicate that two added atoms come from gas. Additionally, it believed reaction involves NiII rather than Ni0 cyclic process based weak attractive interactions between Ni olefin substrate.

Language: Английский

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Recent Advances in Nonprecious Metal Catalysis

Organic Process Research & Development, Journal Year: 2023, Volume and Issue: 27(3), P. 423 - 447

Published: Feb. 17, 2023

Nonprecious-metal-catalyzed alternatives to powerful precious metal transformations are of increasing interest in academia and the pharmaceutical industry due lower cost, better sustainability, toxicity. With continual growth broad field nonprecious catalysis (NPMC), we have chosen highlight selected articles published from March June 2022 which intended examples NPMC that feel may be especially relevant development. We aim inspire academic industrial innovation through discussion herein.

Language: Английский

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Precise Synthesis of ChiralZ‐Allylamides by Cobalt‐Catalyzed Asymmetric Sequential Hydrogenations

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(15)

Published: Feb. 8, 2023

Asymmetric sequential hydrogenations of conjugated enynes have been developed using a Ph-BPE-CoI catalyst for the precise synthesis chiral Z-allylamides in high activity (up to 1000 substrate/catalyst (S/C)) and with excellent enantioselectivity >99 % enantiomeric excess (ee)). Mechanism experiments theoretical calculations support cationic CoI /CoIII redox catalytic cycle. The difference between cobalt complexes Ph-BPE QuinoxP* was explained by process decomposition rate-determining step second hydrogenation.

Language: Английский

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Enantioselective Synthesis of Chiral Cyclic Hydrazines by Ni-Catalyzed Asymmetric Hydrogenation

Organic Letters, Journal Year: 2023, Volume and Issue: 25(20), P. 3644 - 3648

Published: May 15, 2023

An efficient Ni–(S,S)-Ph-BPE complex that catalyzed asymmetric hydrogenation of cyclic N-acyl hydrazones has been developed to produce various chiral hydrazines in high yields with excellent enantioselectivities up >99% enantiomeric excess. Moreover, the can not only proceed smoothly on a gram scale under lower catalyst loading (S/C = 3000) without any decrease enantioselectivity but also be applied synthesis RIP-1 kinase inhibitor.

Language: Английский

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Development of Construction of Chiral C—X Bonds through Nickel Catalyzed Asymmetric Hydrogenation^★

Acta Chimica Sinica, Journal Year: 2023, Volume and Issue: 81(6), P. 646 - 646

Published: Jan. 1, 2023

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 present, this method construction bonds has become prominent trend modern organic chemistry.Among them, development nickel catalysts relatively rapid.Based on this, article will review latest research preparation compounds with via nickel-catalyzed using hydrogen.It divided into five sections consisting C-N, C-O, C-P, C-B C-F by hydrogenation.

Language: Английский

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2,3‐Bis[( R )‐(1,1‐dimethylethyl)methylphosphino]‐Quinoxaline

Encyclopedia of Reagents for Organic Synthesis, Journal Year: 2025, Volume and Issue: unknown, P. 1 - 9

Published: Jan. 3, 2025

Abstract image [ 866081‐62‐1 ] C 18 H 28 N 2 P (MW 334.38) InChI = 1S/C18H28N2P2/c1‐17(2,3)21(7)15‐16(22(8)18(4,5)6)20‐14‐12‐10‐9‐11‐13(14)19‐15/h9‐12H,1‐8H3/t21‐,22‐/m0/s1 InChIKey DRZBLHZZDMCPGX‐VXKWHMMOSA‐N (reagent may be used as a chiral ligand for rhodium, palladium, copper, and silver complexes to perform enantioselective reductions, conjugate additions, allylic alkylations) Alternate Name: QuinoxP*. Physical Data: mp 102–103°C; [α] D −54.3° ( c 1.00, CHCl 3 ); 1 NMR (395.75 MHz, CDCl ) δ 1.00–1.03 (m, ), 1.42–1.44 6 7.70–7.74 8.08–8.12 13 (99.45 4.77 (t, J 4.1 Hz), 27.59 7.4 31.90 129.50, 129.60, 141.63, 165.12 (dd, 5.7, 2.4 Hz); 31 (202.35 δ−17.7 (s); IR (KBr) 2950, 1470, 780 cm −1 ; HRMS (FAB) calcd. 29 (M + H); 335.1809; found: 335.1826. Anal. : C, 64.66; H, 8.44. Found: 64.57; 8.29. Solubility: sol toluene, ether, THF, dichloromethane, hexane. Form Supplied in: orange solid; commercially available. Preparative Methods: solution of n ‐BuLi (1.25 mL 1.60 M hexane solution, 2.0 mmol) was added dropwise stirred t ‐butylmethylphosphine–borane (236 mg, in THF (4 mL) at −78 °C under nitrogen. After 15 min, 2,3‐dichloroquinoxaline (133 0.67 one portion with vigorous stirring the mixture warmed rt during h. additional h, tetramethylethylenediamine (1 continued The reaction quenched HCl extracted combined extracts were washed brine, dried over Na SO 4 . solvent removed vacuum residue purified by chromatography on silica gel (hexane/EtOAc 30/1) give desired product (179 8%) an solid, which further recrystallization from hot MeOH (1.7 cubes. Handling, Storage, Precautions stable air moisture more than 8 months.

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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Solvent-Controlled and Highly Chemoselective Reduction of α,β-Unsaturated Ketones and Aldehydes

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: April 16, 2025

Herein, we establish two highly efficient reductions of α,β-unsaturated ketones and aldehydes via Raney nickel-catalyzed hydrogenation with distinct chemoselectivity, which is controlled by the solvent. This methodology demonstrates a brilliant result when reducing to or alcohols. High isolated yields were obtained for series benzalacetone- cinnamaldehyde-derived substrates without additional column chromatographic purification. The practicability was demonstrated natural products synthesizing approved drug.

Language: Английский

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