Palladium-catalyzed asymmetric hydrophosphination of internal alkynes: Atroposelective access to phosphine-functionalized olefins

Chem, Journal Year: 2022, Volume and Issue: 8(12), P. 3346 - 3362

Published: Sept. 23, 2022

Language: Английский

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Second Generation Catalytic Enantioselective Nucleophilic Desymmetrization at Phosphorus (V): Improved Generality, Efficiency and Modularity

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(18)

Published: Feb. 21, 2024

A broadly improved second generation catalytic two-phase strategy for the enantioselective synthesis of stereogenic at phosphorus (V) compounds is described. This protocol, consisting a bifunctional iminophosphorane (BIMP) catalyzed nucleophilic desymmetrization prochiral, bench stable P(V) precursors and subsequent enantiospecific substitution allows divergent access to wide range C-, N-, O- S- substituted containing from handful enantioenriched intermediates. new ureidopeptide BIMP catalyst/thiaziolidinone leaving group combination allowed far wider substrate scope increased reaction efficiency practicality over previously established protocols. The resulting intermediates could then be transformed into an even greater distinct classes by displacement remaining as well allowing further diversification downstream. Density functional theory (DFT) calculations were performed pinpoint origin enantioselectivity BIMP-catalyzed desymmetrization, rationalize how superior catalyst/leaving leads generality in our second-generation system, shed light onto observed stereochemical retention inversion pathways when performing late-stage S

Language: Английский

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Cobalt‐Catalysed Asymmetric Addition and Alkylation of Secondary Phosphine Oxides for the Synthesis of P‐Stereogenic Compounds

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(52), P. 27241 - 27246

Published: Nov. 5, 2021

The catalytic asymmetric synthesis of P-chiral phosphorus compounds is an important way to construct ligands. Herein, we report a new strategy that adopts the pyridinyl moiety as coordinating group in cobalt-catalysed nucleophilic addition/alkylation secondary phosphine oxides. A series tertiary oxides were generated with up 99 % yield and 99.5 ee, broad functional-group tolerance. Mechanistic studies reveal (R)-secondary preferentially interact cobalt catalysts produce P-stereogenic compounds.

Language: Английский

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Enantioselective Palladium‐Catalyzed Hydrophosphinylation of Allenes with Phosphine Oxides: Access to Chiral Allylic Phosphine Oxides

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(52), P. 27288 - 27292

Published: Sept. 28, 2021

Abstract A Pd‐catalyzed hydrophosphinylation of alkyl and aryl‐oxyallenes with phosphine oxides has been developed for the efficient rapid construction a family chiral allylic diverse range functional groups. This methodology was further applied in facile 2 H ‐chromene later stage functionalization cholesterol.

Language: Английский

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Palladium/Xiao‐Phos‐Catalyzed Kinetic Resolution of sec‐Phosphine Oxides by P‐Benzylation

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(52), P. 27247 - 27252

Published: Oct. 21, 2021

P-stereogenic tert- and sec-phosphines have wide applications in asymmetric catalysis, materials, pharmaceutical chemistry, however, their practical synthesis still constitutes a significant challenge. Herein, successful kinetic resolution of rac-secondary phosphine oxides via the enantioselective P-benzylation process catalyzed by palladium/Xiao-Phos was designed. Both sec-phosphine were delivered good yield excellent enantiopurity (selectivity factor up to 226.1). The appealing synthetic utilities are further demonstrated facile preparation several valuable P-chiral compounds, precursors bidentate ligands, as well transition metal complexes.

Language: Английский

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Ni-catalyzed asymmetric hydrophosphinylation of conjugated enynes and mechanistic studies

Chemical Science, Journal Year: 2022, Volume and Issue: 13(14), P. 4095 - 4102

Published: Jan. 1, 2022

The catalytic asymmetric synthesis of

Language: Английский

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Catalytic Asymmetric Axially Chiral Allenyl C–P Bond Formation

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(28), P. 12619 - 12626

Published: July 8, 2022

Chiral organophosphorous compounds are very important in catalysis, organic syntheses, and medicinal chemistry. However, catalytic enantioselective protocols for the axially chiral allenyl phosphorus have never been reported. Herein, a palladium-catalyzed carbon–phosphorus bond formation reaction affording phosphonates has developed. The enjoys high yields ees accommodating wide range of functional groups. Mechanistic studies unveiled an overwhelming kinetic resolution process.

Language: Английский

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Rh-Catalyzed Regio- and Enantioselective Allylic Phosphinylation

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(7), P. 2893 - 2898

Published: Feb. 14, 2022

Transition-metal-catalyzed branched and enantioselective allylic substitution of monosubstituted precursors with carbon, nitrogen, oxygen, sulfur, fluoride nucleophiles has been well-established. However, such a selective carbon–phosphorus bond formation not realized probably due to the catalyst deactivation by strong coordinating nature phosphinylating reagents. Herein, we report Rh-catalyzed highly regio- synthesis phosphine oxides in presence chiral bisoxazoline-phosphine ligand. The application α-hydroxylalkylphosphine keep low concentration secondary is essential for high yields. addition diphenyl phosphoric acid was found only activate alcohols but also accelerate formation.

Language: Английский

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Copper‐Catalyzed Dynamic Kinetic C−P Cross‐Coupling/Cyclization for the Concise Asymmetric Synthesis of Six‐, Seven‐ and Eight‐MemberedP‐Stereogenic Phosphorus Heterocycles

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(24)

Published: March 29, 2022

Abstract A copper‐catalyzed asymmetric aryl C−P cross‐coupling/cyclization reaction was successfully developed via dynamic kinetic transformation (DYKAT) under mild conditions. This study provides a general and simple method for the catalytic enantioselective synthesis of stable six‐, seven‐ eight‐membered P‐stereogenic phosphorus heterocycles with excellent enantioselectivities moderate to high yields. One‐pot gram‐scale P‐heterocycle from commercially available materials also accomplished enantioselectivity yield.

Language: Английский

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Ni-Catalyzed Enantioselective Benzylation of Secondary Phosphine Oxide

Organic Letters, Journal Year: 2022, Volume and Issue: 24(5), P. 1258 - 1262

Published: Feb. 2, 2022

A nickel-catalyzed benzylic substitution of secondary phosphine oxide was described, affording the dialkylated P-stereogenic tertiary oxides with high to excellent enantioselectivities. The reaction performed under mild conditions commercially available benzyl chlorides and bench stable oxides, exhibiting broad functional group tolerance. It represented a practical example for preparation compounds.

Language: Английский

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