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

et al.

Published: Dec. 5, 2023

A second generation catalytic two-phase strategy for the enantioselective synthesis of chiral at P(V) compounds is described. This protocol, consisting a bifunctional iminophosphorane (BIMP) catalyzed nucleophilic desymmetrization prochiral, bench stable precursors and subsequent enantiospecific substitution allows divergent access to wide range C-, N-, O- S- substituted containing from handful enantioenriched precursors. new catalyst/leaving group combination allowed far wider substrate scope increased reaction efficiency practicality over previously established protocols. The resulting intermediates could then be converted an even greater distinct classes by displacement remaining leaving as well allowing further diversification downstream. Density functional theory (DFT) calculations were performed pinpoint origin enantioselectivity BIMP-catalyzed desymmetrization, rationalize how superior leads generality in our second-generation system, shed light onto observed retention inversion pathways when performing late-stage SN2@P reactions with Grignard reagents.

Language: Английский

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
An overview on copper in industrial chemistry: From ancient pigment to modern catalysis DOI
Mohammad Soleiman‐Beigi, Masoud Mohammadi,

Homa Kohzadi

et al.

Coordination Chemistry Reviews, Journal Year: 2025, Volume and Issue: 529, P. 216438 - 216438

Published: Jan. 17, 2025

Language: Английский

Citations

2
Copper/BINOL-Catalyzed Enantioselective C–H Functionalization toward Planar Chiral Ferrocenes Under Mild Conditions DOI
Zhuo‐Zhuo Zhang, Gang Zhou, Qiang Yue

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(6), P. 4030 - 4039

Published: Feb. 28, 2024

Copper-catalyzed enantioselective C–H activation proceeding through an inner-sphere mechanism remains a huge challenge. Herein, copper-catalyzed alkynylation with terminal alkynes assisted by 8-aminoquinoline using readily available (S)-BINOL as the chiral ligand was disclosed. The reaction proceeded under mild conditions catalytic amount of copper salt, providing range ferrocenes in good yields and enantioselectivities (0 °C, up to 77% yield 94% ee). alteration stoichiometric chemical oxidant renewable electricity is also feasible at ambient temperature, demonstrating robustness this copper/BINOL catalysis. Notably, first cupraelectrocatalyzed reaction. Gram-scale synthesis, versatile transformations, application resulting oxazoline–olefin asymmetric synthesis highlight utility protocols.

Language: Английский

Citations

15
Nickel‐Catalyzed Asymmetric Synthesis of P‐Stereogenic Phosphanyl Hydrazine Building Blocks DOI
Chuanyong Wang,

Qingliang Yang,

Yuan‐Hao Dai

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(46)

Published: Sept. 29, 2023

Catalytic asymmetric methods for the synthesis of synthetically versatile P-stereogenic building blocks offer an efficient and practical approach diversity-oriented preparation P-chiral phosphorus compounds. Herein, we report first nickel-catalyzed secondary aminophosphine-boranes by addition primary phosphines to azo We further demonstrate that P-H P-N bonds on these phosphanyl hydrazine can be reacted sequentially stereospecifically access various compounds with structural diversity.

Language: Английский

Citations

12
Solvent‐Controlled Enantiodivergent Construction of P(V)‐Stereogenic Molecules via Palladium‐Catalyzed Annulation of Prochiral N‐Aryl Phosphonamides with Aromatic Iodides DOI

Qingyu Tian,

Jin Ge,

Yaopeng Liu

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(41)

Published: July 9, 2024

In this work, we describe an efficient and modular method for enantiodivergent accessing P(V)-stereogenic molecules by utilizing the catalytic atroposelective Catellani-type C-H arylation/desymmetric intramolecular N-arylation cascade reaction. The enantioselectivity of protocol was proved to be tuned polarity solvent, thus providing a wide range both chiral enantiomers in moderate good yields with excellent enantiomeric excesses. Noteworthy is that strategy developed herein represents unprecedented example solvent-dictated inversion compounds.

Language: Английский

Citations

4
Copper‐Catalyzed Enantioselective Hydrophosphorylation of Unactivated Alkynes DOI Open Access

Jie Kang,

Kang Ding,

Si‐Mu Ren

et al.

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

Published: Oct. 5, 2024

P-stereogenic phosphorus compounds are essential across various fields, yet their synthesis via enantioselective P-C bond formation remains both challenging and underdeveloped. We report the first copper-catalyzed hydrophosphorylation of alkynes, facilitated by a newly designed chiral 1,2-diamine ligand. Unlike previous methods that rely on kinetic resolution with less than 50 % conversion, our approach employs distinct dynamic asymmetric transformation mechanism, achieving complete conversion racemic starting materials. This reaction is compatible broad range aromatic aliphatic terminal producing products high yields (up to 95 %), exclusive cis selectivity, exceptional regio- enantioselectivity (>20 : 1 r.r. up 96 ee). The resulting were further transformed into diverse array enantioenriched scaffolds. Preliminary mechanistic studies conducted elucidate details.

Language: Английский

Citations

4
Advances in Catalytic Enantioselective Transformations Using Diaryliodonium Reagents DOI

Prasoon Raj Singh,

Arijit Banerjee,

Amit Kumar Simlandy

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 3096 - 3115

Published: Feb. 5, 2025

Language: Английский

Citations

0
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
P(═O)R2-Directed Asymmetric Catalytic C–H Olefination Leading to C–N Axially Chiral Targets DOI

Shengzhou Jin,

Yu Wang, Jun Yan

et al.

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

Published: March 11, 2025

A novel P(═O)R2-directed asymmetric catalytic olefination has been developed, enabling efficient access to carbon–nitrogen axially chiral products with excellent yields (up 92%) and enantioselectivity 99% enantiomeric excess). The synergistic coordination of phosphine oxide functionality l-pGlu-OH the Pd metal center, serving as an directing group ligand, was key success this C–H functionalization system. reaction demonstrated a broad substrate scope, yielding 33 distinct C–N axial products. absolute configuration unambiguously confirmed via X-ray diffraction analysis. Additionally, three representative applications were showcased, involving reduction oxidation produce phosphines related derivatives. plausible cycle mechanism proposed, supported by detailed experimental studies. Aggregates in system identified aggregation-induced polarization experiments.

Language: Английский

Citations

0