Ni-Catalyzed Enantioselective Allylic Alkylation of H-Phosphinates DOI
Qing Zhang, Xu-Teng Liu, Yue Wu

et al.

Organic Letters, Journal Year: 2021, Volume and Issue: 23(22), P. 8683 - 8687

Published: Nov. 4, 2021

The asymmetric synthesis of P-stereogenic phosphinates through allylic alkylation H-phosphinates has been developed. With and acetates as the starting materials, a variety P-chiral were accessed in high enantioselectivities up to 92% ee generally yields. In addition, further study demonstrated applicability this protocol, including scale-up facile transformation chiral products from phosphine oxides with organolithium reagents under mild reaction conditions.

Language: Английский

Ni-Catalyzed Asymmetric Hydrophosphination of Unactivated Alkynes DOI
Xu-Teng Liu,

Xue-Yu Han,

Yue Wu

et al.

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(30), P. 11309 - 11316

Published: July 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.

Language: Английский

Citations

111
Palladium-catalyzed asymmetric hydrophosphination of internal alkynes: Atroposelective access to phosphine-functionalized olefins DOI Creative Commons

Danqing Ji,

Jierui Jing,

Yi Wang

et al.

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

Published: Sept. 23, 2022

Language: Английский

Citations

76
Modular and Facile Access to Chiral α-Aryl Phosphates via Dual Nickel- and Photoredox-Catalyzed Reductive Cross-Coupling DOI

Hepan Wang,

Purui Zheng,

Xiaoqiang Wu

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(9), P. 3989 - 3997

Published: Feb. 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.

Language: Английский

Citations

71
Copper(I)-Catalyzed Asymmetric 1,4-Conjugate Hydrophosphination of α,β-Unsaturated Amides DOI
Yanbo Li, Hu Tian, Liang Yin

et al.

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(47), P. 20098 - 20106

Published: Nov. 11, 2020

A catalytic asymmetric conjugate hydrophosphination of α,β-unsaturated amides is accomplished by virtue the strong nucleophilicity copper(I)-PPh2 species, which provides an array chiral phosphines bearing amide moiety in high to excellent yields with enantioselectivity. Furthermore, dynamic kinetic resolution unsymmetrical diarylphosphines (HPAr1Ar2) successfully carried out through copper(I)-catalyzed addition amides, affords P-chiral good-to-high diastereoselectivity and 1H NMR studies show that precoordination HPPh2 copper(I)-bisphosphine complex critical for efficient deprotonation Barton's Base. Moreover, relative stability copper(I)-(R,RP)-TANIAPHOS presence excessive HPPh2, confirmed 31P studies, pivotal induction, as ligand exchange between bisphosphine would significantly reduce At last, a double furnishes corresponding product yield enantioselectivity, transformed pincer palladium moderate yield. This demonstrated catalyst chalcone.

Language: Английский

Citations

136
Palladium-catalyzed asymmetric hydrophosphorylation of alkynes: facile access to P-stereogenic phosphinates DOI Creative Commons
Zhiping Yang,

Xiaodong Gu,

Li‐Biao Han

et al.

Chemical Science, Journal Year: 2020, Volume and Issue: 11(28), P. 7451 - 7455

Published: Jan. 1, 2020

A catalytic enantioselective synthesis of P-stereogenic alkenylphosphinates is developed through asymmetric hydrophosphorylation. This process demonstrated on racemic phosphinates and leads to diverse directly.

Language: Английский

Citations

105
Organic Superbases in Recent Synthetic Methodology Research DOI

Thomas R. Puleo,

Stephen J. Sujansky,

Shawn E. Wright

et al.

Chemistry - A European Journal, Journal Year: 2020, Volume and Issue: 27(13), P. 4216 - 4229

Published: Aug. 26, 2020

Abstract Organic superbases are a distinct and increasingly utilized class of Brønsted base that possess properties complementary to common inorganic bases. This Concept article discusses recent applications commercial organic in modern synthetic methodologies. Examples the advantages three areas highlighted, including discovery new base‐catalyzed reactions, optimization reactions require stoichiometric base, high‐throughput experimentation technology.

Language: Английский

Citations

97
Copper(I)-Catalyzed Asymmetric Alkylation of Unsymmetrical Secondary Phosphines DOI
Shuai Zhang,

Jun‐Zhao Xiao,

Yanbo Li

et al.

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(26), P. 9912 - 9921

Published: June 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.

Language: Английский

Citations

88
Cobalt‐Catalysed Asymmetric Addition and Alkylation of Secondary Phosphine Oxides for the Synthesis of P‐Stereogenic Compounds DOI

Zeng‐Hua Wu,

An‐Qi Cheng,

Yuan Meng

et al.

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

Citations

78
Palladium/Xiao‐Phos‐Catalyzed Kinetic Resolution of sec‐Phosphine Oxides by P‐Benzylation DOI
Qiang Dai, Lu Liu, Junliang Zhang

et al.

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

Citations

75
Diverse C–P Cross-Couplings of Arylsulfonium Salts with Diarylphosphines via Selective C–S Bond Cleavage DOI
Yun Ye, Jie Zhu, Yinhua Huang

et al.

Organic Letters, Journal Year: 2021, Volume and Issue: 23(6), P. 2386 - 2391

Published: March 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.

Language: Английский

Citations

60