Nickel-Catalyzed Asymmetric Synthesis of Ambiphilic Secondary Phosphine Oxides DOI

Wei-Han Wang,

Siyu Zhang, Yu-Xiang Zhang

et al.

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

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

Xiao‐kang Nie,

Shiqi Zhang, Xuyang Wang

et al.

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

Published: March 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.

Language: Английский

Citations

1
Enantioselective Desymmetrization of Phosphinic Acids via Cu-Catalyzed O-Arylation DOI
Ming Yan, Jiawei Zou, Dongmei Fang

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 4719 - 4725

Published: March 6, 2025

Language: Английский

Citations

0
Catalytic construction of P-stereogenic center via phosphorus-centered nucleophilic substitution DOI
Bingbing Dong, Junmin Zhang, Xiang-Yu Ye

et al.

Chinese Chemical Letters, Journal Year: 2025, Volume and Issue: unknown, P. 111052 - 111052

Published: March 1, 2025

Language: Английский

Citations

0
Nickel-Catalyzed Asymmetric Synthesis of Ambiphilic Secondary Phosphine Oxides DOI

Wei-Han Wang,

Siyu Zhang, Yu-Xiang Zhang

et al.

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

Citations

0