Copper-Phosphido Catalysis: Enantioselective Addition of Phosphines to Cyclopropenes DOI Creative Commons

Brian S. Daniel,

Xintong Hou,

Stephanie A. Corio

et al.

Published: March 24, 2023

We describe a copper-catalyst that promotes the addition of phosphines to cyclopropenes at ambient temperature. A range cyclopropylphosphines bearing different steric and electronic properties can now be accessed in high yields enantioselectivities. combined experimental theoretical mechanistic study supports insertion Cu(I)-phosphido intermediate into strained olefin. Density functional theory calculations reveal migratory as stereodetermining step pathway, with final product formation occurring via syn-protodemetalation. Enrichment phosphorus stereocenters is demonstrated DyKAT process.

Language: Английский

Catalytic Asymmetric Hydrophosphination of α,β-Unsaturated Aza-heteroarenes DOI
Lirong Chen,

Guangfu Lu,

Guiyong Wang

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: April 23, 2025

Here we report a comprehensive investigation of the asymmetric addition diarylphosphorus oxides to wide range α,β-unsaturated pyridines and other N-heterocyclic substrates, catalyzed by commercial chiral phosphoric acid, affording corresponding products in up 99% yield 96% ee. The experimental studies density functional theory calculation suggest possible mechanism role acid control enantioselectivity.

Language: Английский

Citations

0
Modular Assembly of Axially Chiral QUINAP Derivatives via Nickel-Catalyzed Enantioselective C–P Cross-Coupling DOI
Zhiping Yang,

Xiaodong Gu,

Li‐Biao Han

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 8268 - 8273

Published: May 2, 2025

Language: Английский

Citations

0
Chiral PCN pincer Ni(ii) complex-catalyzed asymmetric hydrophosphination of 2-alkenoylpyridines with diphenylphosphine DOI Creative Commons
Jinge Li, Bo Qiu, Hui Jiang

et al.

RSC Advances, Journal Year: 2025, Volume and Issue: 15(20), P. 15904 - 15918

Published: Jan. 1, 2025

Eleven chiral PCN pincer Ni( ii ) complexes were successfully synthesized and characterized. One of them served as an effective stereoselective catalyst for the asymmetric hydrophosphination 2-alkenoylpyridines with diphenylphosphine.

Language: Английский

Citations

0
A Remarkable Catalyst-Free Photochemical Alkene Hydrophosphination with Bis(trimethylsilyl)phosphonite DOI Creative Commons

Eloïse Bréger,

Jade Dussart‐Gautheret, Rachid Taakili

et al.

JACS Au, Journal Year: 2025, Volume and Issue: unknown

Published: June 3, 2025

Language: Английский

Citations

0
A Simple Manganese(I) Catalyst for the Efficient and Selective Hydrophosphination of Olefins with PH3, Primary, and Secondary Phosphanes DOI Creative Commons
Aabid A. Wani, Juan José Gamboa‐Carballo, Harikrishnan Jayaprakash

et al.

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(20)

Published: Feb. 7, 2024

Abstract A tridentate ligand L with a P,NH,N donor motif was synthesized in few steps from commercially available precursors. Upon reaction [MnBr(CO) 5 ], an octahedral 18‐electron complex [Mn(CO) 3 ( )]Br 1 ) is obtained which adopts facial arrangement. After deprotonation of the NH group cationic unit, neutral Mn(I) amido 2 ‐ H )] formed under loss CO. Rearrangement leads to trigonal bipyramidal structure P and N centers are trans position. Further results dep‐blue anionic fragment 2H − ). DFT calculations QTAIM analysis show that contains Mn‐N bond partial double character aromatic MnN C ring. The anion reacts Ph PH give phosphido complex, serves as phosphide transfer reagent activated olefins. But catalytic activity low. However, excellent catalyst loadings low 0.04 mol %, turn over frequencies >40’000 h −1 can be achieved. Furthermore, secondary primary alkyl phosphines well added hydrophosphination wide range olefins such α,β‐unsaturated aldehydes, ketones, esters, nitriles. also, vinyl pyridine some styrene derivatives converted into corresponding phosphanes.

Language: Английский

Citations

2
Diastereoselective and Enantioselective Hydrophosphinylations of Conjugated Enynes, Allenes and Dienes via Synergistic Pd/Co Catalysis DOI

Minhao Tang,

Zhen‐Yu Yang, Aijun Han

et al.

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

Citations

1
Deoxygenative 1,3-Carbophosphination of Allylic Alcohols enabled by Manganese Pincer Catalyst DOI
Xin Chen,

Guanbo Li,

Hui Ma

et al.

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 1, 2024

The first manganese-catalyzed three-component coupling between secondary alcohol, allylic and phosphine via borrowing hydrogen is described. This four-stage, one-pot reaction afforded ε-hydroxy phosphines in a step-economical fashion.

Language: Английский

Citations

1
Copper(I)‐Catalyzed Asymmetric 1,4‐Hydroarsination of α,β‐Unsaturated Compounds DOI

Jun‐Zhao Xiao,

Zhen-Xi Cai,

Zhi‐Zhou Pan

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 18, 2024

Abstract Herein, a copper(I)‐catalyzed asymmetric 1,4‐hydroarsination of β‐substituted α,β‐unsaturated esters is achieved in moderate to excellent yields with high enantioselectivity, based on the proposed nucleophilic [Cu]−AsPh 2 species. As for α‐substituted esters, 1,4‐hydroarsination/enantioselective protonation event occurs smoothly satisfying results. Furthermore, ketone, amide, and phosphine sulfide are well applied present catalytic system. Finally, some control experiments show that HAsPh activated through coordination copper(I) catalyst exhibits inferior soft Lewis basicity HPPh presence copper(I)‐bisphosphine complex.

Language: Английский

Citations

1
Palladium/Azaphos-Catalyzed Asymmetric Suzuki–Miyaura Coupling DOI
Zhiping Yang, Jun Wang,

Yanxin Jiang

et al.

Synthesis, Journal Year: 2023, Volume and Issue: 55(16), P. 2537 - 2542

Published: April 5, 2023

Abstract A palladium-catalyzed asymmetric Suzuki–Miyaura coupling is described with a unique monophosphine ligand, Azaphos. This method provides new ligand framework that could be used in reactions to prepare the axially chiral compounds.

Language: Английский

Citations

2
Palladium‐Catalyzed Enantio‐ and Regioselective Ring‐Opening Hydrophosphinylation of Methylenecyclopropanes DOI Creative Commons
Jian Zhou, Ling Meng, Shujuan Lin

et al.

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 135(26)

Published: April 26, 2023

Abstract Transition metal‐catalyzed hydrofunctionalization of methylenecyclopropanes (MCPs) has presented a considerable challenge due to the difficult manipulation regioselectivity and complicated reaction patterns. Herein, we report straightforward Pd‐catalyzed ring‐opening hydrophosphinylation MCPs via highly selective C−C bond cleavage. This method allows for rapid efficient access wide range chiral allylic phosphine oxides in good yields high enantioselectivities. Additionally, density functional theory (DFT) calculations were performed elucidate mechanism origin enantioselectivity.

Language: Английский

Citations

1