Toolbox for Distal C–H Bond Functionalizations in Organic Molecules

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(6), P. 5682 - 5841

Published: Oct. 18, 2021

Transition-metal-catalyzed C–H activation has developed a contemporary approach to the omnipresent area of retrosynthetic disconnection. Scientific researchers have been tempted take help this methodology plan their synthetic discourses. This paradigm shift helped in development industrial units as well, making synthesis natural products and pharmaceutical drugs step-economical. In vast zone bond activation, functionalization proximal bonds gained utmost popularity. Unlike bonds, distal is more strenuous requires distinctly specialized techniques. review, we compiled various methods adopted functionalize mechanistic insights within each these procedures, scope methodology. With give complete overview expeditious progress made field organic chemistry while also highlighting its pitfalls, thus leaving open for further modifications.

Language: Английский

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Enantioselective Radical Reactions Using Chiral Catalysts

Chemical Reviews, Journal Year: 2022, Volume and Issue: 122(6), P. 5842 - 5976

Published: Jan. 24, 2022

Benefiting from the impressive increase in fundamental knowledge, last 20 years have shown a continuous burst of new ideas and consequently plethora catalytic methods for enantioselective radical reactions. This review aims to provide complete survey progress achieved over this latter period. The first part focuses on use chiral organocatalysts, these include catalysts covalently linked substrate those that interact with by weaker interactions like hydrogen bonds. second is devoted transition-metal redox catalysis which organized according increasing atomic number first-row transition metals (Ti, Cr, Fe, Mn, Co, Ni, Cu). Bioinspired manganese- iron-mediated hydroxylations oxidations are also discussed. A specific section dedicated reactivity Ru, Rh, Ir complexes as Lewis acids special focus at metal. Absorption photons result different events such energy transfer, single-electron hydrogen-atom transfer facilitating formation radicals. Organocatalysis has been successfully combined photocatalysts, opened pathways enlarging precursors available. merger photocatalysis organo- or metalla-photocatalysis brought novelty allowed discovery large original transformations. enzyme-catalyzed reactions involving intermediates largely benefit visible-light irradiation included review. provides comprehensive inventory goal detailing reaction mechanisms involved transformations any nonspecialist could find their own creativity invent yet unknown applications.

Language: Английский

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Catalytic three-component dicarbofunctionalization reactions involving radical capture by nickel

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(19), P. 10836 - 10856

Published: Jan. 1, 2021

The catalytic dicarbofunctionalization of unsaturated π bonds represents a powerful platform for the rapid construction complex motifs. Despite remarkable progress, novel and efficient methods achieving such transformations under milder conditions with chemo-, regio-, stereoselectivity still remain significant challenge; thus, their development is highly desirable. Recently, merging nickel catalysis radical chemistry offers new benign unprecedented reactivity selectivity. In this review, we summarize recent advances in area by underpinning domino involving capture to provide clear overview reaction designs mechanistic scenarios.

Language: Английский

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General Method for Enantioselective Three-Component Carboarylation of Alkenes Enabled by Visible-Light Dual Photoredox/Nickel Catalysis

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(48), P. 20390 - 20399

Published: Nov. 19, 2020

A visible-light-promoted photoredox/nickel protocol for the enantioselective three-component carboarylation of alkenes with tertiary and secondary alkyltrifluoroborates aryl bromides is described. This redox-neutral allows facile divergent access to a wide array enantioenriched β-alkyl-α-arylated carbonyls, phosphonates, sulfones in high yields excellent enantioselectivities from readily available starting materials. We also report modular synthesis flurbiprofen analogs piragliatin lead compound demonstrate synthetic utility. Experimental computational mechanistic studies were performed gain insights into mechanism origin chemo- enantioselectivity.

Language: Английский

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Nickel and Palladium Catalysis: Stronger Demand than Ever

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(2), P. 1180 - 1200

Published: Jan. 5, 2022

Key similarities and differences of Pd Ni in catalytic systems are discussed. Overall, catalyze a vast number similar C–C C–heteroatom bond-forming reactions. However, the smaller atomic radius lower electronegativity Ni, as well more negative redox potentials low-valent species, often provide higher reactivity oxidative addition or insertion reactions persistence alkyl-Ni intermediates against β-hydrogen elimination, thus enabling activation reluctant electrophiles, including alkyl electrophiles. Another key point relates to stability open-shell electronic configurations Ni(I) Ni(III) compared with Pd(I) Pd(III). Nickel very involve interconvertible Ni(n+) active species variable oxidation states (Ni(0), Ni(I), Ni(II), Ni(III)). In contrast, involving Pd(III) still relatively less developed may require facilitation by special ligands merging photo- electrocatalysis. high Pd(n+) ensure their facile reduction Pd(0) under assistance numerous reagents solvents, providing concentrations molecular Pd1(0) complexes that can reversibly aggregate into Pdn clusters nanoparticles form cocktail Pdn(0) various nuclearities (i.e., values "n"). Ni(0) strong reductants; they sensitive deactivation air other oxidizers and, consequence, operate at catalyst loadings than palladium same The ease robustness versatility for catalysis, whereas variety enables diverse uncommon reactivity, albeit requiring efforts stabilization nickel systems. As discussion, we note easily "cocktail particles" different but (Pd1, Pdn, NPs), behave species" is stable nuclearities. Undoubtedly, there stronger demand ever not only develop improved efficient catalysts also understand mechanisms

Language: Английский

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The interplay of carbophilic activation and Au(i)/Au(iii) catalysis: an emerging technique for 1,2-difunctionalization of C–C multiple bonds

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(18), P. 10422 - 10450

Published: Jan. 1, 2021

This review highlights a decade-long journey of Au-catalyzed 1,2-difunctionalization reactions C–C multiple bonds that have been realized due to the productive integration Au( i )/Au( iii )catalysis with unique π-activation mode gold complexes.

Language: Английский

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Ni-Catalyzed Ligand-Controlled Regiodivergent Reductive Dicarbofunctionalization of Alkenes

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(27), P. 10282 - 10291

Published: June 24, 2021

Transition-metal-catalyzed dicarbofunctionalization of alkenes involving intramolecular Heck cyclization followed by intermolecular cross-coupling has emerged as a powerful engine for building heterocycles with sterically congested quaternary carbon centers. However, only exo-cyclization/cross-coupling products can be obtained; endo-selective cyclization/cross-coupling not been reported yet and still poses formidable challenge. We herein report the first example catalyst-controlled regiodivergent synthesis five- six-membered benzo-fused lactams bearing all-carbon Using chiral Pyrox- or Phox-type bidentate ligand, 5-exo cyclization/cross-couplings proceed favorably to produce indole-2-ones in good yields excellent regioselectivity enantioselectivities (up 98% ee). When C6-carboxylic acid-modified 2,2′-bipyridine was used 3,4-dihydroquinolin-2-ones were obtained through 6-endo-selective processes. This transformation is modular tolerant variety functional groups. The ligand rather than substrate structures precisely dictates pattern. Moreover, synthetic value this protocol demonstrated preparation biologically relevant molecules structural scaffolds.

Language: Английский

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Recent advances in difunctionalization of alkenes using pyridinium salts as radical precursors

Chemical Communications, Journal Year: 2022, Volume and Issue: 58(24), P. 3847 - 3864

Published: Jan. 1, 2022

This review summarises recent applications of pyridinium salts in radical-mediated difunctionalization alkenes. We hope this will provide a comprehensive overview topic and promote the wider development application salts.

Language: Английский

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N-Heterocyclic carbenes as privileged ligands for nickel-catalysed alkene functionalisation

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 52(9), P. 2946 - 2991

Published: Jan. 1, 2023

This review discusses the applications of N-heterocyclic carbene ligands and their influence on reactivity selectivity Ni-catalysed alkene functionalisations.

Language: Английский

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Direct synthesis of unprotected aryl C-glycosides by photoredox Ni-catalysed cross-coupling

Nature Synthesis, Journal Year: 2023, Volume and Issue: 2(3), P. 251 - 260

Published: Jan. 16, 2023

Language: Английский

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