Thiourea-Assisted Chiral Bicyclic Imidazole Organocatalysts: Design, Synthesis, and Application in Asymmetric Acylative Desymmetrization of Bisphenols for the Construction of P-Stereocenters DOI
Chenglong Hu, Xuyang Tang,

Baochi Zhang

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(24), P. 16300 - 16306

Published: Dec. 6, 2023

Thiourea-assisted chiral bicyclic imidazole organocatalysts were designed, synthesized, and successfully applied in the asymmetric acylative desymmetrization of P-prochiral bisphenols. Under mild conditions, P-stereogenic products obtained high yields (up to 99% yield) with enantioselectivities ee). Most importantly, reaction could also achieve satisfactory results under 1 mol % catalyst loadings. Mechanistic studies showed that synergistic effect including covalent activation acyl group by nucleophilic noncovalent H-bonding π-interaction between substrate was crucial for efficient construction P-stereocenters.

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
Catalytic enantioselective nucleophilic desymmetrization of phosphonate esters DOI Creative Commons
Michele Formica, Tatiana Rogova, Heyao Shi

et al.

Nature Chemistry, Journal Year: 2023, Volume and Issue: 15(5), P. 714 - 721

Published: May 1, 2023

Molecules that contain a stereogenic phosphorus atom are crucial to medicine, agrochemistry and catalysis. While methods available for the selective construction of various chiral organophosphorus compounds, catalytic enantioselective approaches their synthesis far less common. Given vastness possible substituent combinations around atom, protocols preparation should also be divergent, providing facile access not only one but many classes compounds. Here we introduce strategy an enantioenriched phosphorus(V) centre can diversified enantiospecifically wide range biologically relevant The process, which involves nucleophilic substitution catalysed by superbasic bifunctional iminophosphorane catalyst, accommodate carbon substituents at phosphorus. resulting stable, yet versatile, synthetic intermediates combined with multitude medicinally O-, N- S-based nucleophiles.

Language: Английский

Citations

53
P-Stereogenic Phosphorus Ligands in Asymmetric Catalysis DOI
Tsuneo Imamoto

Chemical Reviews, Journal Year: 2024, Volume and Issue: 124(14), P. 8657 - 8739

Published: July 2, 2024

Chiral phosphorus ligands play a crucial role in asymmetric catalysis for the efficient synthesis of useful optically active compounds. They are largely categorized into two classes: backbone chirality and P-stereogenic ligands. Most reported belong to former class. Privileged ones such as BINAP DuPhos frequently employed wide range catalytic transformations. In contrast, latter class has remained small family many years mainly because their synthetic difficulty. The late 1990s saw emergence novel with superior enantioinduction ability Rh-catalyzed hydrogenation reactions. Since then, numerous have been synthesized used This Review summarizes thus far, including stereochemical electronic properties that afford high excellent enantioselectivities. Examples reactions use this described together applications construction key intermediates natural products therapeutic agents. literature covered dates back 1968 up until December 2023, centering on studies published later years.

Language: Английский

Citations

41
Second Generation Catalytic Enantioselective Nucleophilic Desymmetrization at Phosphorus (V): Improved Generality, Efficiency and Modularity DOI Creative Commons
Michele Formica, Branislav Ferko, T. R. Marsh

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(18)

Published: Feb. 21, 2024

A broadly improved second generation catalytic two-phase strategy for the enantioselective synthesis of stereogenic at phosphorus (V) compounds is described. This protocol, consisting a bifunctional iminophosphorane (BIMP) catalyzed nucleophilic desymmetrization prochiral, bench stable P(V) precursors and subsequent enantiospecific substitution allows divergent access to wide range C-, N-, O- S- substituted containing from handful enantioenriched intermediates. new ureidopeptide BIMP catalyst/thiaziolidinone leaving group combination allowed far wider substrate scope increased reaction efficiency practicality over previously established protocols. The resulting intermediates could then be transformed into an even greater distinct classes by displacement remaining as well allowing further diversification downstream. Density functional theory (DFT) calculations were performed pinpoint origin enantioselectivity BIMP-catalyzed desymmetrization, rationalize how superior catalyst/leaving leads generality in our second-generation system, shed light onto observed stereochemical retention inversion pathways when performing late-stage S

Language: Английский

Citations

16
Construction of P‐Chiral Alkenylphosphine Oxides through Highly Chemo‐, Regio‐, and Enantioselective Hydrophosphinylation of Alkynes DOI
Qiang Dai, Lu Liu,

Yanyan Qian

et al.

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 59(46), P. 20645 - 20650

Published: Aug. 5, 2020

Abstract Alkenylphosphine oxides have a wide spectrum of practical applications. However, chemo‐, regio‐, and enantiocontrolled construction this structural motif still constitutes significant synthetic challenge. Here we show that these compounds can be efficiently accessed by using palladium/Xiao‐Phos catalytic system, which leads to the highly regioselective formation anti‐Markovnikov adducts through addition secondary phosphine oxide an alkyne. Diverse (hetero)aryl alkyl alkynes, as well both terminal internal alkynes employed substrates. The kinetic resolution process makes it possible produce alkenylphosphine recovered with high ee values. Further transformations two P‐chiral scaffolds confirm practicability application prospect our strategies. Initial mechanistic studies strongly suggested hydropalladation is likely responsible for conversion process.

Language: Английский

Citations

113
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
Recent developments in highly efficient construction of P-stereogenic centers DOI Creative Commons
Xinyi Ye,

Lin Peng,

Xiaoze Bao

et al.

Green Synthesis and Catalysis, Journal Year: 2020, Volume and Issue: 2(1), P. 6 - 18

Published: Dec. 25, 2020

The construction of chiral phosphorus molecules with asymmetric center on the atom has always been considered to be challenging in synthetic chemistry. Such P-stereogenic compounds possess many unique properties allowing potential applications natural products synthesis, pharmaceuticals as well ligands organometallic catalysis. This increasing importance driven chemists develop sophisticated strategies over years construct compounds. In this review, we aim discuss methodologies for centers that were developed from 2005 2020. review organized into seven sections according their respective reaction principles beginning desymmetrization, followed by phosphonoalkylation and phosphonoarylation, addition, deprotonation, ring-closing metathesis, use organolithiums Grignard reagents together auxiliaries ending kinetic resolution.

Language: Английский

Citations

82
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
Cobalt/Salox‐Catalyzed Enantioselective Dehydrogenative C−H Alkoxylation and Amination DOI
Jiahao Chen,

Ming‐Ya Teng,

Fan‐Rui Huang

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(38)

Published: Aug. 2, 2022

The past decade has witnessed a rapid progress in asymmetric C-H activation. However, the enantioselective alkoxylation and amination with alcohols free amines remains elusive. Herein, we disclose first dehydrogenative enabled by simple cobalt/salicyloxazoline (Salox) catalysis. use of cheap readily available cobalt(II) salts as catalysts Saloxs chiral ligands provides an efficient method to access P-stereogenic compounds excellent enantioselectivities (up >99 % ee). practicality this protocol is demonstrated gram-scale preparation further derivatizations resulting phosphinamides, which offering flexible alternative mono- diphosphine ligands. Preliminary mechanistic studies on reaction suggest that cobalt(III/IV/II) catalytic cycle might be involved.

Language: Английский

Citations

62
Ni-catalyzed asymmetric hydrophosphinylation of conjugated enynes and mechanistic studies DOI Creative Commons
Yaqian Zhang,

Xue-Yu Han,

Yue Wu

et al.

Chemical Science, Journal Year: 2022, Volume and Issue: 13(14), P. 4095 - 4102

Published: Jan. 1, 2022

The catalytic asymmetric synthesis of

Language: Английский

Citations

54