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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Enantioselective Synthesis of P-Chiral Phosphine Oxides Bearing an All-Carbon Quaternary Stereogenic Center via Palladium-Catalyzed Domino Heck–Suzuki Reaction

ACS Catalysis, Journal Year: 2024, Volume and Issue: unknown, P. 14762 - 14768

Published: Sept. 20, 2024

Language: Английский

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Enantioselective Synthesis of Five to Eight‐Membered P‐Stereogenic Benzo‐Fused Heterocycles via Copper‐Catalyzed Dynamic Kinetic Resolution

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(10), P. 2285 - 2291

Published: March 6, 2024

Abstract P‐stereogenic benzo‐fused heterocycles is a privileged skeleton due to their outstanding catalytic properties and bioactivities. However, enantioselective synthesis still underdeveloped. Here we demonstrate the use of easily accessible racemic H−P(O) compounds as starting materials commercial chiral N 1 , 2 ‐dimethyl‐1,2‐diphenylethane‐1,2‐diamine ligand in combination with Cu(I) catalysts enable an attractive dynamic kinetic C( sp 2)−P cross‐coupling reaction. This protocol not only exhibits broad substrate scope but also provides general access diverse range useful five‐, six‐, seven‐ eight‐membered O, P‐ containing good high yields enantioselectivities.

Language: Английский

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Nickel-Catalyzed Asymmetric Synthesis of Ambiphilic Secondary Phosphine Oxides

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: April 16, 2025

The synthesis of ambiphilic compounds, which possess both strong nucleophilic and electrophilic functional groups, presents a significant challenge due to their propensity self-react, forming oligomers or polymers. We have successfully achieved the nickel-catalyzed asymmetric P-stereogenic alkenyl secondary phosphine oxides from tailored primary oxide by leveraging controversial stability reactivity. This method demonstrates remarkable tolerance toward wide range unactivated alkynes, including those derived natural products medicinally relevant molecules, thus providing universal synthon for phosphines with high enantioselectivity regioselectivity. product exhibits interesting orthogonal reactivities nucleophiles electrophiles can be easily converted variety compounds.

Language: Английский

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Diastereoselective and Enantioselective Hydrophosphinylations of Conjugated Enynes, Allenes and Dienes via Synergistic Pd/Co Catalysis

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 137(1)

Published: Sept. 10, 2024

Abstract Different from the reported work focusing on construction of single P ‐ or C ‐stereocenter via hydrophosphinylation unsaturated carbon bonds, highly diastereo‐ and enantioselective reaction allenes, conjugated enynes 1,3‐dienes is achieved a designed Pd/Co dual catalysis newly modified masked phosphinylating reagent. A series allyl motifs bearing both tertiary are prepared in generally good yields, >20 : 1 dr, rr 99 % ee. The unprecedented 1,3‐enynes established to generate skeletons containing nonadjacent chiral axis. first stereodivergent also developed achieve all four ‐containing stereoisomers. present protocol features use only 3‐minutes time 0.1 catalyst, with observation up 730 TON. set mechanistic studies reveal necessity roles two metal catalysts corroborate synergistic process.

Language: Английский

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Nickel-Catalyzed Enantioselective Alkylation of Primary Phosphines

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

Published: Sept. 26, 2024

Functional molecules derived from stereogenic phosphorus centers have important applications in the discovery of drugs and agrochemicals. They are also widely utilized as chiral ligands or organocatalysts for diverse asymmetric transformations. However, access to P-stereogenic motifs has always been regarded a highly challenging yet desirable goal organic synthesis. The development general practical methods stereoselective construction synthetically versatile P(III)-stereogenic phosphines is particularly appealing but remains elusive. Herein, we describe nickel-catalyzed alkylation primary with alkyl halides synthesis secondary phosphine-boranes high enantioselectivity broad substrate scope. resulting optically active allow further stereospecific transformations, thereby establishing modular efficient platform diversity-oriented phosphine compounds.

Language: Английский

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Synthesis of P-Stereogenic Phosphinamides via Nickel-Catalyzed Kinetic Resolution of H-Phosphinamides by Alkenylation and Arylation

Organic Letters, Journal Year: 2024, Volume and Issue: 26(41), P. 8662 - 8667

Published: Oct. 4, 2024

A nickel-catalyzed enantioselective cross-coupling for the synthesis of P-stereogenic phosphinamides has been developed. The asymmetric alkenylation and arylation racemic H-phosphinamides using alkenyl aryl bromides resulted in formation N-phosphinyl compounds with good yields high enantioselectivities. This method tolerates a variety functional groups, its applications are explored through scale-up reactions product transformations.

Language: Английский

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Methods for functionalization of anthraquinones

Russian Chemical Reviews, Journal Year: 2024, Volume and Issue: 93(10), P. RCR5141 - RCR5141

Published: Oct. 1, 2024

Language: Английский

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Diastereoselective and Enantioselective Hydrophosphinylations of Conjugated Enynes, Allenes and Dienes via Synergistic Pd/Co Catalysis

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 64(1)

Published: Sept. 10, 2024

Different from the reported work focusing on construction of single P- or C-stereocenter via hydrophosphinylation unsaturated carbon bonds, highly diastereo- and enantioselective reaction allenes, conjugated enynes 1,3-dienes is achieved a designed Pd/Co dual catalysis newly modified masked phosphinylating reagent. A series allyl motifs bearing both tertiary C- P-stereocenter are prepared in generally good yields, >20 : 1 dr, rr 99 % ee. The unprecedented 1,3-enynes established to generate skeletons containing nonadjacent chiral axis. first stereodivergent also developed achieve all four P-containing stereoisomers. present protocol features use only 3-minutes time 0.1 catalyst, with observation up 730 TON. set mechanistic studies reveal necessity roles two metal catalysts corroborate synergistic process.

Language: Английский

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Advances in Chiral Pincer Complexes: Insights and Applications in Catalytic Asymmetric Reactions

International Journal of Molecular Sciences, Journal Year: 2024, Volume and Issue: 25(19), P. 10344 - 10344

Published: Sept. 26, 2024

Chiral pincer complexes, characterized by their rigid tridentate coordination framework, have emerged as powerful catalysts in asymmetric synthesis. This review provides a comprehensive overview of recent advancements the development chiral pincer-type ligands and corresponding transition metal complexes. We highlight latest progress application across range catalytic reactions, including (transfer) hydrogenation polar non-polar bonds, hydrophosphination, alkynylation, Friedel-Crafts enantioselective reductive cyclization alkynyl-tethered cyclohexadienones, hydrosilylation, well Aza–Morita–Baylis–Hillman reactions. The structural rigidity tunability complexes enable precise control over stereoselectivity, resulting high enantioselectivity efficiency complex molecular transformations. As field advances, innovations ligand design exploration new centers are expected to expand scope utility these catalysts, bearing significant implications for synthesis enantioenriched compounds pharmaceuticals, materials science, beyond.

Language: Английский

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