Copper‐Catalyzed Dynamic Kinetic Asymmetric P−C Coupling of Secondary Phosphine Oxides and Aryl Iodides

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(25)

Опубликована: Апрель 14, 2023

Abstract Transition‐metal‐catalyzed enantioselective P−C cross‐coupling of secondary phosphine oxides (SPOs) is an attractive method for synthesizing P ‐stereogenic phosphorus compounds, but the development such a dynamic kinetic asymmetric process remains considerable challenge. Here we report unprecedented highly intermolecular coupling SPOs and aryl iodides catalyzed by copper complexes ligated finely modified chiral 1,2‐diamine ligand. The reaction tolerates wide range iodides, affording tertiary (TPOs) in high yields with good enantioselectivity (average 89.2 % ee). resulting enantioenriched TPOs were transformed into structurally diverse ‐chiral scaffolds, which are valuable as ligands catalysts synthesis.

Язык: Английский

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Synthesis of P‐Stereogenic Phosphine Oxides via Nickel‐Catalyzed Asymmetric Cross‐Coupling of Secondary Phosphine Oxides with Alkenyl and Aryl Bromides

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(15)

Опубликована: Фев. 14, 2023

Abstract A general and mild nickel‐catalyzed enantioselective C(sp 2 )−P cross‐coupling for synthesizing P‐stereogenic phosphine oxides has been developed. The asymmetric alkenylation/arylation of racemic secondary with alkenyl/aryl bromides generated high yields enantioselectivities. Various functional groups were tolerated, the applications this method demonstrated through late‐stage functionalization product transformations.

Язык: Английский

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Catalytic Asymmetric Hydrophosphinylation of 2‐Vinylazaarenes to Access P‐Chiral 2‐Azaaryl‐Ethylphosphine Oxides

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(16)

Опубликована: Фев. 22, 2023

A chiral Brønsted acid-catalysed asymmetric hydrophosphinylation of 2-vinylazaarenes by secondary phosphine oxides is described. variety P-chiral 2-azaaryl-ethylphosphine are synthesized with high yields and ees, which both the substituents phosphines azaarenes can be flexibly modulated, underscoring an exceptionally broad scope substrates. These adducts valuable to metal catalysis since resultant tertiary from reduction them verified as a kind effective C1 -symmetric 1,5-hybrid P,N-ligands. Importantly, this platform enables generic efficient kinetic resolution oxides. It thus provides expedient approach access enantiomers derived hydrophosphinylation, further improving utility method.

Язык: Английский

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Ni^II-Catalyzed Enantioselective Anti-Markovnikov Hydrophosphination of Unactivated Alkynes

ACS Catalysis, Год журнала: 2023, Номер 13(10), С. 6994 - 7001

Опубликована: Май 9, 2023

A mechanism-inspired, reaction mode-controlled enantio- and regioselective anti-Markovnikov hydrophosphination of unactivated alkynes was accomplished by NiII catalysis. Alkenyl phosphine products could be obtained with high regio- enantioselectivity easily derivatized to structurally diverse chiral compounds. Mechanistic studies on both Ni0-catalyzed Markovnikov addition NiII-catalyzed have been carried out combining experimental computational methods. In the Ni0 system, an allyl nickel complex as catalyst resting state whose structure unambiguously determined single-crystal XRD analysis. sequential hydrometallation, ligand exchange, reductive elimination mechanism elucidated corroboratively DFT calculations. cationic secondary serves active catalyst. migratory insertion protonation sequence operative accomplish hydrophosphination.

Язык: Английский

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Kinetic Resolution of α,β-Unsaturated Tertiary Phosphine Oxides via Alkene E → Z Isomerization Catalyzed by a Photoexcited Chiral Copper Complex

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 4541 - 4549

Опубликована: Март 3, 2025

Язык: Английский

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Catalytic Enantioselective Nucleophilic Desymmetrization at Phosphorus(V): A Three-Phase Strategy for Modular Preparation of Phosphoramidates

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Март 19, 2025

Chiral phosphoramidates characterized by at least a P–N bond without P–C demonstrate significant applicative value within nucleoside phosphoramidate prodrugs. Despite the availability of methodologies for selective construction diverse chiral organophosphorus entities, achieving P-stereocenters solely substituted heteroatoms often relies on diastereomeric synthesis. Here, we present catalytic enantioselective desymmetrization strategy using an electrophilic phosphorus reagent with three leaving groups as substrate, enabling three-phase nucleophilic attack various alcohols and amines. By generating broad range possible substituent combinations around atoms, this synthetic may expedite synthesis screening biologically active phosphoramidates.

Язык: Английский

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A Ni-catalyzed asymmetric C(sp)–P cross-coupling reaction for the synthesis of P-stereogenic alkynylphosphines

Chemical Science, Год журнала: 2023, Номер 14(5), С. 1286 - 1290

Опубликована: Янв. 1, 2023

Due to the high reactivity of triple bond, P-stereogenic alkynylphosphines could be easily derivatized, serving as universal building blocks for structurally diverse phosphine compounds. However, synthesis via direct P-C bond formation was unprecedented. Here, we report an efficient method with enantioselectivity a Ni-catalyzed asymmetric cross-coupling reaction. The reaction tolerate variety functional groups, affording products that can converted into useful derivatives.

Язык: Английский

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Catalytic asymmetric Tsuji–Trost α−benzylation reaction of N-unprotected amino acids and benzyl alcohol derivatives

Nature Communications, Год журнала: 2022, Номер 13(1)

Опубликована: Май 6, 2022

Abstract Catalytic asymmetric Tsuji–Trost benzylation is a promising strategy for the preparation of chiral benzylic compounds. However, only few such transformations with both good yields and enantioselectivities have been achieved since this reaction was first reported in 1992, its use current organic synthesis restricted. In work, we N-unprotected amino acid esters as nucleophiles reactions benzyl alcohol derivatives. A ternary catalyst comprising aldehyde, palladium species, Lewis used to promote reaction. Both mono- polycyclic alcohols are excellent reagents. Various unnatural optically active α-benzyl acids produced good-to-excellent enantioselectivities. This catalytic method formal two somatostatin mimetics proposed structure natural product hypoestestatin 1. mechanism that plausibly explains stereoselective control proposed.

Язык: Английский

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Transition metal-catalyzed enantioselective C–P coupling reactions for the construction of P-stereogenic centers

Chem Catalysis, Год журнала: 2022, Номер 2(11), С. 2876 - 2888

Опубликована: Ноя. 1, 2022

Язык: Английский

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Nickel-catalysed enantioselective reaction of secondary phosphine oxides and activated vinylcyclopropanes

Organic & Biomolecular Chemistry, Год журнала: 2023, Номер 21(15), С. 3096 - 3100

Опубликована: Янв. 1, 2023

Activated vinylcyclopropanes can form zwitterionic π-allylmetal species in the presence of transition metals and are widely used organic synthesis. A nickel-catalyzed asymmetric allylation secondary phosphine oxides with was described. Tertiary oxide products could be obtained up to 91% yield 92% ee.

Язык: Английский

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