Recent Developments in Enantioselective Transition Metal Catalysis Featuring Attractive Noncovalent Interactions between Ligand and Substrate

ACS Catalysis, Journal Year: 2020, Volume and Issue: 10(18), P. 10672 - 10714

Published: Aug. 14, 2020

Enantioselective transition metal catalysis is an area very much at the forefront of contemporary synthetic research. The development processes that enable efficient synthesis enantiopure compounds unquestionable importance to chemists working within many diverse fields central science. Traditional approaches solving this challenge have typically relied on leveraging repulsive steric interactions between chiral ligands and substrates in order raise energy one diastereomeric states over other. By contrast, Review examines alternative tactic which a set attractive noncovalent operating are used control enantioselectivity. Examples where creative approach has been successfully applied render fundamental enantioselective presented discussed. In cases examined, ligand scaffold carefully designed accommodate these interactions, while others, critical was only elucidated subsequent computational mechanistic studies. Through exploration discussion recent reports encompassing wide range reaction classes, we hope inspire continue develop asymmetric transformations based powerful concept.

Language: Английский

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Ni-Catalyzed Asymmetric Hydrophosphination of Unactivated Alkynes

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

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Palladium-catalyzed asymmetric hydrophosphination of internal alkynes: Atroposelective access to phosphine-functionalized olefins

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

Published: Sept. 23, 2022

Language: Английский

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Recent Progress in Cyclic Aryliodonium Chemistry: Syntheses and Applications

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(4), P. 1364 - 1416

Published: Jan. 17, 2023

Hypervalent aryliodoumiums are intensively investigated as arylating agents. They excellent surrogates to aryl halides, and moreover they exhibit better reactivity, which allows the corresponding arylation reactions be performed under mild conditions. In past decades, acyclic aryliodoniums widely explored However, unmet need for is improvement of their notoriously low reaction economy because coproduced iodides during often wasted. Cyclic have intrinsic advantage in terms economy, started receive considerable attention due valuable synthetic applications initiate cascade reactions, can enable construction complex structures, including polycycles with potential pharmaceutical functional properties. Here, we summarizing recent advances made research field cyclic aryliodoniums, nascent design aryliodonium species applications. First, general preparation typical diphenyl iodoniums described, followed by heterocyclic monoaryl iodoniums. Then, initiated arylations coupled subsequent domino summarized construct polycycles. Meanwhile, building biaryls axial atropisomers discussed a systematic manner. Finally, very advance employed halogen-bonding organocatalysts described.

Language: Английский

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Catalytic enantioselective nucleophilic desymmetrization of phosphonate esters

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

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Pd-Catalyzed Asymmetric Larock Indole Synthesis to Access Axially Chiral N-Arylindoles

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(8), P. 5493 - 5501

Published: Feb. 13, 2024

Larock indole synthesis is one of the most straightforward and efficient methods for indoles; however, there has been no asymmetric version yet construction indole-based axially chiral N-arylindoles since its initial report in 1991. Herein we first example an by employing a sulfinamide phosphine (SadPhos) ligand (Ming-Phos) with palladium. It allows rapid wide range N-arylindole compounds good yields up to 98:2 er. The application this unique scaffold as organocatalyst promising. Furthermore, kinetic study revealed that alkyne migratory insertion rate-determining step, which proven density functional theory (DFT) calculations. Additionally, DFT studies also suggest N–C dihedral difference caused steric hindrance contributes enantioselectivity control.

Language: Английский

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Second Generation Catalytic Enantioselective Nucleophilic Desymmetrization at Phosphorus (V): Improved Generality, Efficiency and Modularity

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

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Rapid Synthesis of Chiral 1,2‐Bisphosphine Derivatives through Copper(I)‐Catalyzed Asymmetric Conjugate Hydrophosphination

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 59(18), P. 7057 - 7062

Published: Feb. 17, 2020

1,2-Bisphosphines have been identified as one class of important and powerful chiral ligands in asymmetric catalysis with transition metals. Herein, a copper(I)-catalyzed hydrophosphination α,β-unsaturated phosphine sulfides was developed the assistance "soft-soft" interaction between copper(I)-catalyst sulfide moiety, which afforded 1,2-bisphosphine derivatives diversified electronic nature steric hindrance high to excellent yields enantioselectivity. Moreover, challenging catalytic hydrophosphination/protonation reaction achieved Strikingly, dynamic kinetic resolution racemic diarylphosphines also successfully carried out diastereo- enantioselectivities. Interestingly, nucleophilic copper(I)-diphenylphosphide species characterized by 31 P NMR spectrum mass spectrum. At last, three products were transformed 1,2-bisphosphines, employed Rh-catalyzed hydrogenation α-amino-α,β-unsaturated ester. The α-amino acid derivative produced enantioselectivity, demonstrated utility present methodology.

Language: Английский

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Construction of P‐Chiral Alkenylphosphine Oxides through Highly Chemo‐, Regio‐, and Enantioselective Hydrophosphinylation of Alkynes

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

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Introducing Chirality at Phosphorus Atoms: An Update on the Recent Synthetic Strategies for the Preparation of Optically Pure P‐Stereogenic Molecules

European Journal of Organic Chemistry, Journal Year: 2020, Volume and Issue: 2020(23), P. 3351 - 3366

Published: April 30, 2020

The synthesis of phosphorus molecules presenting a chiral center on the P‐atom, also known as P‐stereogenic compounds, has long attracted curiosity scientific community. Indeed, these chemical compounds feature many peculiar properties, allowing their use in various fields applications, ranging from medicine to enantioselective catalysis. However, synthesis, and more particularly introduction retention information center, remains very challenging task. That is why this review article focuses recent advances molecules, with particular focus atom. This summarizes main synthetic approaches directed towards such entities historical perspective. Thus, based auxiliaries attached atom stoichiometric reagents will be discussed first, they were historically first developed. Then, discoveries catalytic direct optical resolution P‐chiral discussed.

Language: Английский

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