Enantioselective C−H Activation with Earth‐Abundant 3d Transition Metals

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 58(37), P. 12803 - 12818

Published: May 11, 2019

Molecular syntheses largely rely on time- and labour-intensive prefunctionalization strategies. In contrast, C-H activation represents an increasingly powerful approach that avoids lengthy of prefunctionalized substrates, with great potential for drug discovery, the pharmaceutical industry, material sciences, crop protection, among others. The enantioselective functionalization omnipresent bonds has emerged as a transformative tool step- atom-economical generation chiral molecular complexity. However, this rapidly growing research area remains dominated by noble transition metals, prominently featuring toxic palladium, iridium rhodium catalysts. Indeed, despite significant achievements, use inexpensive sustainable 3d metals in asymmetric activations is still clearly its infancy. Herein, we discuss remarkable recent progress transformations via organometallic base up to April 2019.

Language: Английский

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Transition Metal Catalyzed Enantioselective C(sp²)–H Bond Functionalization

ACS Catalysis, Journal Year: 2020, Volume and Issue: 10(23), P. 13748 - 13793

Published: Nov. 12, 2020

Direct catalytic transformation of C–H bonds to new functionalities has provided a powerful strategy synthesize complex molecular scaffolds in straightforward way. Unstinting efforts the synthetic community have helped overcome long-standing major challenge regioselectivity by introducing directing group concept. However, full potential cannot be realized unless activated are stereochemically controlled. The enantioselective bond functionalization could provide an imperative tool for sustainable way synthesizing chiral scaffolds. Despite intrinsic challenges achieving stereocontrol, developed different tools order achieve stereoselective functionalization. In this review, we discuss remarkable recent advances emerging area C(sp2)–H highlight and opportunities, emphasizing techniques so far.

Language: Английский

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Enantioselective C H Bond Functionalizations by 3d Transition-Metal Catalysts

Trends in Chemistry, Journal Year: 2019, Volume and Issue: 1(5), P. 471 - 484

Published: April 20, 2019

Language: Английский

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Diverse Approaches for Enantioselective C−H Functionalization Reactions Using Group 9 Cp^xM^III Catalysts

Chemistry - A European Journal, Journal Year: 2020, Volume and Issue: 26(33), P. 7346 - 7357

Published: Jan. 29, 2020

Transition-metal-catalyzed C-H functionalization reactions with Cp*MIII catalysts (M=Co, Rh, Ir) have found a wide variety of applications in organic synthesis. Albeit the intrinsic difficulties achieving catalytic stereocontrol using these due to their lack additional coordination sites for external chiral ligands and conformational flexibility Cp ligand, enantioselective Group 9 metal triad Cp-type been intensively studied since 2012. In this minireview, progress according type catalyst used are summarized discussed. The development Cpx complexes thereof, artificial metalloenzymes, carboxylate-assisted activations, alkylations assisted by carboxylic acids or sulfonates, transient directing groups

Language: Английский

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Chiral Cyclopentadienyl Cobalt(III) Complexes Enable Highly Enantioselective 3d-Metal-Catalyzed C–H Functionalizations

Journal of the American Chemical Society, Journal Year: 2019, Volume and Issue: 141(14), P. 5675 - 5680

Published: March 22, 2019

The synthesis of a set cobalt(III)-complexes equipped with trisubstituted chiral cyclopentadienyl ligands is reported, and their steric electronic parameters are mapped. application potential these complexes for asymmetric C-H functionalizations 3d-metals shown by the dihydroisoquinolones from N-chlorobenzamides broad range alkenes. transformation proceeds excellent enantioselectivities up to 99.5:0.5 er high regioselectivities. observed values outperform best rhodium(III)-based methods this reaction type. Moreover, challenging substrates such as alkyl alkenes also react regio- enantioselectivities.

Language: Английский

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Dioxazolones: Stable Substrates for the Catalytic Transfer of Acyl Nitrenes

ACS Catalysis, Journal Year: 2020, Volume and Issue: 10(8), P. 4751 - 4769

Published: March 30, 2020

Dioxazolones are a convenient class of acyl nitrene transfer reagents. Their application in homogeneous transition-metal catalysis has led to many new amidation reactions. typically activated by transition metals at relatively low reaction temperatures. The metal nitrenoids formed decarboxylative activation dioxazolones generally electron deficient and commonly react concerted fashion. "Intermolecular" insertion reactions involving preactivated C–H bonds ("inner-sphere" mechanism) easily compete with the Curtius-type rearrangement, but for intramolecular "direct" transfer/insertion nonpreactivated substrates (i.e., without preceding formation metal–carbon or metal–hydride bonds) extensive ligand optimization is important prevent such unwanted side ease dioxazolone synthesis, CO2 gas as sole byproduct from dioxazolones, importance general development several interesting producing N-aryl amides, oxazoles, lactams. Since proceeds under mild conditions, stereo- enantioselective also possible, which useful synthesis bioactive nitrogen-containing compounds. This review provides an overview these reported recent years.

Language: Английский

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Nitrene transfer catalysts for enantioselective C–N bond formation

Nature Reviews Chemistry, Journal Year: 2021, Volume and Issue: 5(8), P. 580 - 594

Published: June 28, 2021

Language: Английский

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Atroposelective Synthesis of Axially Chiral Styrenes via an Asymmetric C–H Functionalization Strategy

Chem, Journal Year: 2020, Volume and Issue: 6(2), P. 497 - 511

Published: Jan. 9, 2020

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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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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