Divergent Synthesis of Tunable Cyclopentadienyl Ligands and Their Application in Rh-Catalyzed Enantioselective Synthesis of Isoindolinone

Journal of the American Chemical Society, Год журнала: 2020, Номер 142(16), С. 7379 - 7385

Опубликована: Апрель 7, 2020

A series of rhodium complexes bearing sterically and electronically tunable cyclopentadienyl ligands, prepared by utilizing Co2(CO)8-mediated [2+2+1] cyclization as a key step, were synthesized. In the presence 2.5 mol% CpmRh4, unprecedented enantioselective [4+1] annulation reaction benzamides alkenes was achieved with broad substrate scope under mild conditions, providing variety isoindolinones excellent regio- enantioselectivity (up to 94% yield, 97:3 er). Preliminary mechanistic studies suggest that involves an oxidative Heck intramolecular alkene hydroamination reaction.

Язык: Английский

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Rhodium-Catalyzed Asymmetric C–H Functionalization Reactions

Chemical Reviews, Год журнала: 2023, Номер 123(16), С. 10079 - 10134

Опубликована: Авг. 1, 2023

This review summarizes the advancements in rhodium-catalyzed asymmetric C–H functionalization reactions during last two decades. Parallel to rapidly developed palladium catalysis, rhodium catalysis has attracted extensive attention because of its unique reactivity and selectivity reactions. In recent years, Rh-catalyzed have been significantly many respects, including catalyst design, reaction development, mechanistic investigation, application synthesis complex functional molecules. presents an explicit outline catalysts ligands, mechanism, scope coupling reagents, applications.

Язык: Английский

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Ni-Catalyzed Asymmetric Hydrophosphination of Unactivated Alkynes

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(30), С. 11309 - 11316

Опубликована: Июль 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.

Язык: Английский

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Enantioselective [3+2] Annulation of Aldimines with Alkynes by Scandium‐Catalyzed C−H Activation

Angewandte Chemie International Edition, Год журнала: 2025, Номер unknown

Опубликована: Янв. 3, 2025

Abstract The enantioselective [3+2] annulation of readily accessible aldimines with alkynes via C−H activation is, in principle, a straightforward and atom‐efficient route for synthesizing chiral 1‐aminoindenes, which are important components wide array natural products, bioactive molecules, functional materials. However, such asymmetric transformation has remained undeveloped to date due the lack suitable catalysts. Here, we report first time using half‐sandwich scandium This protocol enabled synthesis diverse multi‐substituted 1‐aminoindene derivatives 100 % atom‐efficiency, broad substrate scope, high regio‐ enantioselectivity. Density theory (DFT) analyses have revealed that noncovalent C−H⋅⋅⋅π interaction between tert ‐Bu substituent cyclopentadienyl (Cp) ligand phenyl ring an aromatic aldimine played role achieving level work not only offers efficient selective new family but also unprecedented insights into enantioselectivity control Cp‐ligated metal

Язык: Английский

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Chiral Carboxylic Acid Enabled Achiral Rhodium(III)‐Catalyzed Enantioselective C−H Functionalization

Angewandte Chemie International Edition, Год журнала: 2018, Номер 57(37), С. 12048 - 12052

Опубликована: Июль 24, 2018

Reported is an achiral Cpx RhIII /chiral carboxylic acid catalyzed asymmetric C-H alkylation of diarylmethanamines with a diazomalonate, followed by cyclization and decarboxylation to afford 1,4-dihydroisoquinolin-3(2H)-one. Secondary alkylamines as well nonprotected primary underwent the transformation high enantioselectivities (up 98.5:1.5 e.r.) using newly developed chiral sole source chirality achieve enantioselective cleavage concerted metalation-deprotonation mechanism.

Язык: Английский

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Efficient Kinetic Resolution of Sulfur‐Stereogenic Sulfoximines by Exploiting Cp^XRh^III‐Catalyzed C−H Functionalization

Angewandte Chemie International Edition, Год журнала: 2019, Номер 58(26), С. 8902 - 8906

Опубликована: Май 2, 2019

Abstract Chiral sulfoximines with stereogenic sulfur atoms are promising motifs in drug discovery. We report an efficient method to access chiral through a C−H functionalization based kinetic resolution. A rhodium(III) complex equipped Cp x ligand selectively participates conjunction phthaloyl phenylalanine the activation of just one two sulfoximine enantiomers. The intermediate reacts various diazo compounds, providing 1,2‐benzothiazines synthetically valuable substitution patterns. Both and were obtained high yields excellent enantioselectivity, s ‐values up 200. utility is illustrated by synthesis key intermediates pharmacologically relevant kinase inhibitors.

Язык: Английский

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Ni-Catalyzed Asymmetric Allylation of Secondary Phosphine Oxides

Journal of the American Chemical Society, Год журнала: 2019, Номер 141(42), С. 16584 - 16589

Опубликована: Окт. 6, 2019

A nickel-catalyzed asymmetric allylation of secondary phosphine oxides (SPO) for the synthesis tertiary (TPO) was realized with high enantioselectivity. The dynamic kinetic transformation SPO accomplished in presence nickel complex. By elucidating absolute configurations reacted starting material and TPO product, we confirmed that reaction proceeded through a P-stereo retention process. protocol represents first example synthesizing P-stereogenic by reaction.

Язык: Английский

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Enantioselective Formal C(sp³)−H Bond Activation in the Synthesis of Bioactive Spiropyrazolone Derivatives

Angewandte Chemie International Edition, Год журнала: 2018, Номер 58(1), С. 307 - 311

Опубликована: Окт. 17, 2018

Abstract Herein, we report the first enantioselective annulation of α‐arylidene pyrazolones through a formal C(sp 3 )−H activation under mild conditions enabled by highly variable Rh III ‐Cp x catalysts. The method has wide substrate scope and proceeds with good to excellent yields enantioselectivities. Its synthetic utility was demonstrated late‐stage functionalization drugs natural products as well preparation enantioenriched [3]dendralenes. Preliminary biological investigations also identified spiropyrazolones novel class Hedgehog pathway inhibitors.

Язык: Английский

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Catalytic Enantioselective Methylene C(sp³)−H Amidation of 8‐Alkylquinolines Using a Cp*Rh^III/Chiral Carboxylic Acid System

Angewandte Chemie International Edition, Год журнала: 2019, Номер 58(50), С. 18154 - 18158

Опубликована: Окт. 8, 2019

Catalytic enantioselective directed methylene C(sp3 )-H amidation reactions of 8-alkylquinolines using a Cp*RhIII /chiral carboxylic acid (CCA) hybrid catalytic system are described. A binaphthyl-based chiral efficiently differentiates between the enantiotopic C-H bonds, which leads to formation C-N bonds with good enantioselectivity.

Язык: 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, Год журнала: 2020, Номер 2020(23), С. 3351 - 3366

Опубликована: Апрель 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.

Язык: Английский

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