Ni-Catalyzed Asymmetric Hydrophosphination of Unactivated Alkynes

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(30), С. 11309 - 11316

Опубликована: Июль 20, 2021

The practical synthesis of P-stereogenic tertiary phosphines, which have wide applications in asymmetric catalysis, materials, and pharmaceutical chemistry, represents a significant challenge. A regio- enantioselective hydrophosphination using cheap ubiquitous alkynes catalyzed by nickel complex was designed, the toxic air-sensitive secondary phosphines were prepared situ from bench-stable phosphine oxides. This methodology has been demonstrated with unprecedented substrate scope functional group compatibility to afford electronically structurally diversified P(III) compounds. products could be easily converted into various precursors bidentate ligands organocatalysts, as well variety transition-metal complexes containing both P- metal-stereogenic centers.

Язык: Английский

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

Chem, Год журнала: 2022, Номер 8(12), С. 3346 - 3362

Опубликована: Сен. 23, 2022

Язык: Английский

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Modular and Facile Access to Chiral α-Aryl Phosphates via Dual Nickel- and Photoredox-Catalyzed Reductive Cross-Coupling

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(9), С. 3989 - 3997

Опубликована: Фев. 22, 2022

Chiral phosphine-containing skeletons are important motifs in bioactive natural products, pharmaceuticals, chiral catalysts, and ligands. Herein, we report a general modular platform to access α-aryl phosphorus compounds via Ni/photoredox-catalyzed enantioconvergent reductive cross-coupling between α-bromophosphates aryl iodides. This dual catalytic regime exhibited high efficiency good functional group compacity. A wide variety of substrates bearing diverse set groups could be converted into phosphates excellent yields enantioselectivities. The utility the method was also demonstrated by development new phosphine ligand synthesis enzyme inhibitor derivatives. detailed mechanistic studies supported radical chain process revealed unique distinction compared with traditional cross-coupling.

Язык: Английский

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Copper(I)-Catalyzed Asymmetric Alkylation of Unsymmetrical Secondary Phosphines

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(26), С. 9912 - 9921

Опубликована: Июнь 23, 2021

A copper(I)-catalyzed asymmetric alkylation of HPAr1Ar2 with alkyl halides is uncovered, which provides an array P-stereogenic phosphines in generally high yield and enantioselectivity. The electrophilic enjoy a broad substrate scope, including allyl bromides, propargyl bromide, benzyl iodides. Moreover, 11 unsymmetrical diarylphosphines (HPAr1Ar2) serve as competent pronucleophiles. present methodology also successfully applied to catalytic double triple alkylation, the corresponding products were obtained moderate diastereo- excellent enantioselectivities. Some 31P NMR experiments indicate that bulky HPPhMes exhibits weak competitively coordinating ability Cu(I)-bisphosphine complex, thus presence stoichiometric does not affect enantioselectivity significantly. Therefore, this reaction attributed performance unique Cu(I)-(R,RP)-TANIAPHOS complex induction. Finally, one monophosphine two bisphosphines prepared by are employed efficient chiral ligands afford three structurally diversified Cu(I) complexes, demonstrates synthetic utility methodology.

Язык: 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, Год журнала: 2021, Номер 60(52), С. 27241 - 27246

Опубликована: Ноя. 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.

Язык: Английский

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

Angewandte Chemie International Edition, Год журнала: 2021, Номер 60(52), С. 27288 - 27292

Опубликована: Сен. 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.

Язык: Английский

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

Angewandte Chemie International Edition, Год журнала: 2021, Номер 60(52), С. 27247 - 27252

Опубликована: Окт. 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.

Язык: Английский

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Manganese(I)-Catalyzed H–P Bond Activation via Metal–Ligand Cooperation

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(48), С. 20071 - 20076

Опубликована: Ноя. 19, 2021

Here we report that chiral Mn(I) complexes are capable of H-P bond activation. This activation mode enables a general method for the hydrophosphination internal and terminal α,β-unsaturated nitriles. Metal-ligand cooperation, strategy previously not considered catalytic activation, is at base mechanistic action Mn(I)-based catalyst. Our computational studies support stepwise mechanism provide insight into origin enantioselectivity.

Язык: Английский

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Diverse C–P Cross-Couplings of Arylsulfonium Salts with Diarylphosphines via Selective C–S Bond Cleavage

Organic Letters, Год журнала: 2021, Номер 23(6), С. 2386 - 2391

Опубликована: Март 10, 2021

Diverse C-P cross-couplings of arylthianthrenium salts with diarylphosphines producing various triarylphosphines via highly selective C-S bond cleavage are reported. In the absence catalyst, reaction undergoes phosphinative ring opening exclusively an endocyclic a thianthrene skeleton. The use palladacycle catalyst under otherwise same conditions enables phosphination exocyclic significantly higher speed.

Язык: Английский

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Asymmetric C–H Activation for the Synthesis of P- and Axially Chiral Biaryl Phosphine Oxides by an Achiral Cp*Ir Catalyst with Chiral Carboxylic Amide

ACS Catalysis, Год журнала: 2021, Номер 12(1), С. 193 - 199

Опубликована: Дек. 14, 2021

The catalytic synthesis of P- and axially chiral biaryl phosphine oxides was realized via the Cp*Ir-catalyzed asymmetric C–H coupling tertiary substituted with diarylacetylenes. carboxylic amides were used to control stereoselectivity in activation, enabling construction up 96% ee. Transformation products into trivalent ligands has also been demonstrated.

Язык: Английский

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