Synthesis of Axially Chiral Styrenes through Pd‐Catalyzed Asymmetric C−H Olefination Enabled by an Amino Amide Transient Directing Group

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 59(16), P. 6576 - 6580

Published: Feb. 3, 2020

Abstract The atroposelective synthesis of axially chiral styrenes remains a formidable challenge due to their relatively lower rotational barriers compared the biaryl atropoisomers. Herein, we describe construction through Pd II ‐catalyzed C−H olefination, using bulky amino amide as transient auxiliary. Various were produced with good yields and high enantioselectivity (up 95 % yield 99 ee ). Carboxylic acid derivatives resulting showed superior enantiocontrol over counterparts in Co III enantioselective C(sp 3 )−H amidation thioamide. Mechanistic studies suggest that cleavage is enantioselectivity‐determining step.

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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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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Rhodium-Catalyzed Asymmetric C–H Functionalization Reactions

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(16), P. 10079 - 10134

Published: Aug. 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.

Language: Английский

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Enantioselective desymmetrization reactions in asymmetric catalysis

Tetrahedron, Journal Year: 2022, Volume and Issue: 106-107, P. 132629 - 132629

Published: Jan. 1, 2022

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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Cobalt(III)-Catalyzed Enantioselective C–H Functionalization: Ligand Innovation and Reaction Development

Accounts of Chemical Research, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 26, 2025

ConspectusIn contrast to precious transition metals, such as palladium and rhodium, the development of novel chiral ligands for enantioselective C-H functionalizations catalyzed by earth-abundant, cost-effective, environmentally friendly 3d metals poses substantial challenges, primarily due variable oxidation states, intricate coordination patterns, limited mechanistic insights. In this Account, we summarize our research endeavors in three types Co(III) catalysis: pseudotetrahedral achiral Cp*Co(III)/chiral carbonyl acid (CCA) catalysis, situ-generated octahedral cobalt(III) via cobalt/salicyloxazoline (Salox) Co(II)/chiral phosphoric (CPA) cooperative achieved through strategic ligand design. Our initial objective was achieve functionalization Cp*Co(III) catalysts with external ligands, aiming circumvent laborious preparation CpxCo(III) complexes. To end, developed several CCA incorporating non-covalent interactions (NCIs) a crucial design element. Next, address limitations associated lengthy synthesis Cp-ligated complexes difficulties modification, explored concept situ generation catalysis using commercially available cobalt(II) salts tailor-made ligands. This exploration led two innovative catalytic systems, namely, Co(II)/Salox Co(II)/CCA sequential catalysis. The emerged versatile strategy, demonstrating excellent enantioselectivities across range asymmetric reactions construct various molecules central, axial, planar, inherent chirality. facile single step, along ease further enhances versatility applicability approach. Moreover, successfully applied cobalt/Salox electro- photochemical-catalyzed functionalization, electrons or oxygen traceless oxidant, thereby eliminating need stoichiometric chemical oxidants. Through studies reaction developments, elucidated detailed structure-enantioselectivity relationships which are expected inform future endeavors. Finally, Co(II)/CPA enabled spiro-γ-lactams olefination/asymmetric [4 + 1] spirocyclization. Mechanistically, establishment stereochemistry occurs during cyclization where CPA serves both neutral Brønsted acid, stereoinduction independent cleavage step. We anticipate that insights advancements Account will inspire innovations drive progress metal-catalyzed reactions.

Language: Английский

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Enantiodivergent Desymmetrization in the Rhodium(III)‐Catalyzed Annulation of Sulfoximines with Diazo Compounds

Angewandte Chemie International Edition, Journal Year: 2018, Volume and Issue: 57(47), P. 15534 - 15538

Published: Oct. 11, 2018

RhIII - and IrIII -catalyzed asymmetric C-H functionalization reactions of arenes have relied on the employment chiral /IrIII cyclopentadienyl catalysts, introduction carboxylic acids to achiral Cp*RhX2 integration both strategies. Despite considerable progress, each reaction only provided a specific configuration enantioenriched product when using particular catalyst. Reported in this work is enantiodivergent coupling sulfoximines with various diazo compounds by desymmetrizing annulation. The enantiodivergence was enabled judicious choice acids, enantioselectivity correlates steric bias acid sulfoximine.

Language: 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, Journal Year: 2019, Volume and Issue: 58(26), P. 8902 - 8906

Published: May 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.

Language: Английский

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