Catalytic Enantioselective Functionalizations of C–H Bonds by Chiral Iridium Complexes

Chemical Reviews, Journal Year: 2020, Volume and Issue: 120(18), P. 10516 - 10543

Published: Sept. 8, 2020

The development of catalytic enantioselective transformations, enabling the construction complex molecular scaffolds from simple precursors, has been a long-standing challenge in organic synthesis. Recent achievements transition-metal catalyzed functionalizations carbon–hydrogen (C–H) bonds represent promising pathway toward this goal. Over last two decades, iridium catalysis evolved as valuable tool stereocontrolled synthesis chiral molecules via C–H activation. iridium-based systems with various ligand classes, well studies their reaction mechanisms, resulted dynamic progress area. This review aims to present comprehensive picture by complexes emphasis on mechanisms activation step.

Language: Английский

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Efficient Synthesis of Sulfur-Stereogenic Sulfoximines via Ru(II)-Catalyzed Enantioselective C–H Functionalization Enabled by Chiral Carboxylic Acid

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(18), P. 6810 - 6816

Published: April 28, 2021

Ru(II)-catalyzed enantioselective C-H functionalization involving an enantiodetermining cleavage step remains undeveloped. Here we describe a activation/annulation of sulfoximines with α-carbonyl sulfoxonium ylides using novel class chiral binaphthyl monocarboxylic acids as ligands, which can be easily and modularly prepared from 1,1'-binaphthyl-2,2'-dicarboxylic acid. A broad range sulfur-stereogenic were in high yields excellent enantioselectivities (up to 99% yield ee) via desymmetrization, kinetic resolution, parallel resolution. Furthermore, the resolution products transformed sulfoxides key intermediates for kinase inhibitors.

Language: Английский

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Forging C−heteroatom bonds by transition-metal-catalyzed enantioselective C–H functionalization

Chem, Journal Year: 2021, Volume and Issue: 8(2), P. 384 - 413

Published: Dec. 17, 2021

Language: Английский

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Chiral Carboxylic Acid Assisted Enantioselective C–H Activation with Achiral Cp^xM^III (M = Co, Rh, Ir) Catalysts

ACS Catalysis, Journal Year: 2021, Volume and Issue: 11(11), P. 6455 - 6466

Published: May 17, 2021

Enantioselective C–H functionalization is a powerful tool for synthesizing chiral molecules. In the past few years, combination of high-valent group 9 metals with achiral Cpx ligands and carboxylic acids (CCA) has emerged as promising catalytic system to enable selective cleavage enantiotopic bonds. This Perspective summarizes background, catalyst design, applied reactions in detail, followed by discussion future directions.

Language: Английский

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Cobalt(III)/Chiral Carboxylic Acid‐Catalyzed Enantioselective Synthesis of Benzothiadiazine‐1‐oxides via C−H Activation

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(28)

Published: May 2, 2022

Abstract Among sulfoximine derivatives containing a chiral sulfur center, benzothiadiazine‐1‐oxides are important for applications in medicinal chemistry. Here, we report that the combination of an achiral cobalt(III) catalyst and pseudo‐ C 2 ‐symmetric H 8 ‐binaphthyl carboxylic acid enables asymmetric synthesis from sulfoximines dioxazolones via enantioselective C−H bond cleavage. With optimized protocol, with several functional groups can be accessed high enantioselectivity.

Language: Английский

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Electrooxidative Rhodium(III)/Chiral Carboxylic Acid‐Catalyzed Enantioselective C−H Annulation of Sulfoximines with Alkynes

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(15)

Published: Jan. 30, 2024

Abstract The combination of achiral Cp*Rh(III) with chiral carboxylic acids (CCAs) represents an efficient catalytic system in transition metal‐catalyzed enantioselective C−H activation. However, this hybrid catalysis is limited to redox‐neutral activation reactions and the adopt oxidative remains elusive pose a significant challenge. Herein, we describe development electrochemical Cp*Rh(III)‐catalyzed annulation sulfoximines alkynes enabled by acid (CCA) operationally friendly undivided cell at room temperature. A broad range enantioenriched 1,2‐benzothiazines are obtained high yields excellent enantioselectivities (up 99 % yield 98 : 2 er). practicality method demonstrated scale‐up reaction batch reactor external circulation. crucial intermediate isolated, characterized, transformed, providing rational support for Rh(III)/Rh(I) electrocatalytic cycle.

Language: Английский

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Enantioselective C–H Alkenylation of Ferrocenes with Alkynes by Half-Sandwich Scandium Catalyst

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(6), P. 2470 - 2476

Published: Feb. 2, 2021

The enantioselective C–H alkenylation of ferrocenes with alkynes is, in principle, a straightforward and atom-efficient route for the construction planar-chiral ferrocene scaffolds bearing alkene functionality but has remained scarcely explored to date. Here we report first time highly quinoline- pyridine-substituted by half-sandwich scandium catalyst. This protocol features broad substrate scope, high enantioselectivity, 100% atom efficiency, selectively affording new family N/alkene functionalities. mechanistic details have been clarified DFT analyses. use quinoline/alkene-functionalized product as chiral ligand asymmetric catalysis is also demonstrated.

Language: Английский

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Cp*Co(III)-Catalyzed Enantioselective Hydroarylation of Unactivated Terminal Alkenes via C–H Activation

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(45), P. 19112 - 19120

Published: Nov. 8, 2021

Enantioselective hydroarylation of unactivated terminal akenes constitutes a prominent challenge in organic chemistry. Herein, we reported Cp*Co(III)-catalyzed asymmetric aliphatic alkenes assisted by new type tailor-made amino acid ligands. Critical to the chiral induction was engaging novel noncovalent interaction (NCI), which has seldomly been disclosed C-H activation area, arising from molecular recognition among organocobalt(III) intermediate, coordinated alkene, and well-designed ligand. A broad range C2-alkylated indoles were obtained high yields excellent enantioselectivities. DFT calculations revealed reaction mechanism elucidated origins stereodetermining alkene insertion step.

Language: Английский

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Facile synthesis of axially chiral styrene-type carboxylic acids via palladium-catalyzed asymmetric C–H activation

Chemical Science, Journal Year: 2021, Volume and Issue: 12(10), P. 3726 - 3732

Published: Jan. 1, 2021

Palladium-catalyzed asymmetric C–H functionalization to yield axially chiral styrene-type carboxylic acids is described, in which axial chirality and sterically hindered group were incorporated one-step.

Language: Английский

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Development of Pseudo-C₂-symmetric Chiral Binaphthyl Monocarboxylic Acids for Enantioselective C(sp³)–H Functionalization Reactions under Rh(III) Catalysis

ACS Catalysis, Journal Year: 2021, Volume and Issue: 11(7), P. 4271 - 4277

Published: March 22, 2021

Enantioselective C(sp3)–H functionalization reactions using high-valent group 9 metal catalysts with cyclopentadienyl ligands have been achieved by the introduction of appropriate chiral carboxylic acids. However, diversity acids, as well that applicable substrate structures remains limited. Herein, we report pseudo-C2-symmetric tunable acids a binaphthyl backbone and their application to enantioselective amidation 2-alkylpyridines related heteroaromatic substrates. The fixed cyclic structure pseudo-C2-symmetry developed would reduce conformational flexibility ambiguity. combination an optimal acid sterically hindered rhodium catalyst (Cp*tBuRhIII) exhibited high enantioselectivity (up 96:4 er).

Language: Английский

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