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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Ligand-controlled stereodivergent alkenylation of alkynes to access functionalized trans- and cis-1,3-dienes

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: Jan. 4, 2023

Precise stereocontrol of functionalized alkenes represents a long-standing research topic in organic synthesis. Nevertheless, the development catalytic, easily tunable synthetic approach for stereodivergent synthesis both E-selective and even more challenging Z-selective highly substituted 1,3-dienes from common substrates remains underexploited. Here, we report photoredox nickel dual catalytic strategy sulfonylalkenylation terminal alkynes with vinyl triflates sodium sulfinates under mild conditions. With judicious choice simple catalyst ligand, this method enables efficient divergent access to Z- E-sulfonyl-1,3-dienes same set starting materials. This features broad substrate scope, good functional compatibility, excellent chemo-, regio-, stereoselectivity. Experimental DFT mechanistic studies offer insights into observed stereoselectivity controlled by ligands.

Language: Английский

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Carbon quaternization of redox active esters and olefins by decarboxylative coupling

Science, Journal Year: 2024, Volume and Issue: 384(6691), P. 113 - 118

Published: April 4, 2024

The synthesis of quaternary carbons often requires numerous steps and complex conditions or harsh reagents that act on heavily engineered substrates. This is largely a consequence conventional polar-bond retrosynthetic disconnections in turn require multiple functional group interconversions, redox manipulations, protecting chemistry. Here, we report simple catalyst reductant combination converts two types feedstock chemicals, carboxylic acids olefins, into tetrasubstituted through quaternization radical intermediates. An iron porphyrin activates each substrate by electron transfer hydrogen atom transfer, then combines the fragments using bimolecular homolytic substitution (S

Language: Английский

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Cross-Electrophile Coupling: Principles, Methods, and Applications in Synthesis

Chemical Reviews, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 26, 2024

Cross-electrophile coupling (XEC), defined by us as the cross-coupling of two different σ-electrophiles that is driven catalyst reduction, has seen rapid progression in recent years. As such, this review aims to summarize field from its beginnings up until mid-2023 and provide comprehensive coverage on synthetic methods current state mechanistic understanding. Chapters are split type bond formed, which include C(sp

Language: Английский

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Synthesis of C-glycosides by Ti-catalyzed stereoselective glycosyl radical functionalization

Chem, Journal Year: 2021, Volume and Issue: 7(12), P. 3377 - 3392

Published: Oct. 13, 2021

Language: Английский

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Recent Advances in First-Row Transition Metal-Catalyzed Reductive Coupling Reactions for π-Bond Functionalization and C-Glycosylation

Accounts of Chemical Research, Journal Year: 2023, Volume and Issue: 56(22), P. 3292 - 3312

Published: Nov. 2, 2023

ConspectusEfficient construction of ubiquitous carbon-carbon bonds between two electrophiles has garnered interest in recent decades, particularly if it is mediated by nonprecious, first-row transition metals. Reductive coupling advantages over traditional cross-coupling obviating the need for stoichiometric air- and moisture-sensitive organometallic reagents. By harnessing metal-catalyzed reductive as a powerful tool, intricate molecular architectures can be readily assembled through installation C-C across π systems (alkenes/alkynes) via reaction with appropriate electrophiles. Despite advances alkene difunctionalization, there remains significant potential discovery novel pathways. In this regard, development protocols that enable union challenging alkyl/alkynyl high regio- chemoselectivity highly sought-after goal.Apart from π-bond functionalization, found application carbohydrate chemistry, synthesis valuable C-glycosyl compounds. vein, suitable glycosyl donors used to generate reactive radical intermediates under conditions. Through elaborately designed reactions, these trapped furnish pharmaceutically relevant glycoconjugates. Consequently, diversification compound using metal catalysis holds strong appeal.In Account, we summarize our efforts reactions applications alkene/alkyne functionalization C-glycosylation. We will first discuss nickel (Ni)-catalyzed difunctionalization alkenes, aided an 8-aminoquinoline (AQ) directing auxiliary. Next, highlight Ni-catalyzed hydroalkylation alkenyl amides tethered similar AQ-derived Lastly, efficient 1,3-enynes involving site- stereoselective terminal alkynes alkynyl halides NHPI esters.Beyond dicarbofunctionalization, extended paradigm toward C-glycosidic linkages carbohydrates. employing earth-abundant iron (Fe)-based catalyst, show useful radicals generated chlorides These captured bond formation C-aryl, C-alkenyl, C-alkynyl compounds diastereoselectivity. Our multicomponent chlorides, aryl/alkyl iodides, isobutyl chloroformate conditions led C-acyl glycosides. addition Fe Ni, discovered Ti-catalyzed/Mn-promoted synthetic route access C-alkyl C-alkenyl compounds, electron-deficient alkenes/alkynes. further developed electron donor-acceptor (EDA) photoactivation system leveraging decarboxylative deaminative strategies C-glycosylation Ni catalysis. This approach been demonstrated selectively activate carboxyl amino motifs glycopeptide conjugates. Finally, distinct catalytic transformations bench-stable heteroaryl sulfones, achieved stereodivergent both α- β-anomers C-aryl glycosides, one which involves aryl iodides.The findings presented Account are anticipated have far-reaching implications beyond research. foresee results pave way new founded on concept coupling, leading future.

Language: Английский

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Ni-catalyzed ligand-controlled divergent and selective synthesis

Science China Chemistry, Journal Year: 2023, Volume and Issue: 66(11), P. 2951 - 2976

Published: May 5, 2023

Language: Английский

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Unlocking Diverse π-Bond Enrichment Frameworks by the Synthesis and Conversion of Boronated Phenyldiethynylethylenes

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(14), P. 10167 - 10176

Published: March 27, 2024

The π-bond enrichment frameworks not only serve as a crucial building block in organic synthesis but also assume pivotal role the fields of materials science, biomedicine, photochemistry, and other related disciplines owing to their distinctive structural characteristics. incorporation various substituents into C═C double bonds tetrasubstituted alkenes is currently highly significant research area. However, with diverse on poses challenge achieving stereoselectivity. Here, we reported an efficient convergent route Cu-catalyzed borylalkynylation both symmetrical unsymmetrical 1,3-diynes, B2pin2, acetylene bromide construction boronated phenyldiethynylethylene (BPDEE) derivatives excellent chemo-, stereo-, regioselectivities. BPDEE could transform novel π-conjugated gem-diphenyldiethynylethylene (DPDEE), vinylphenyldiethynylethylene (VPDEE), phenyltriethynylethylene (PTEE) by stepwise process, which provides flexible platform for complex that were difficult synthesize previous methods. initial optical characterization revealed synthesized molecules exhibited aggregation-induced emission (AIE) properties, further establishes groundwork future applications enriches advances field functional research.

Language: Английский

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Divergent Synthesis of [3,4]-Fused 3-Alkenyl-Oxindoles via Propargyl Alcohol-Triggered C(sp³)–H Functionalization

ACS Catalysis, Journal Year: 2021, Volume and Issue: 12(2), P. 943 - 952

Published: Dec. 30, 2021

[3,4]-Fused oxindoles are the core structures of naturally occurring oxindole alkaloids, and fused tricyclic have distinguished themselves with unique biological activities. Herein, we developed a synthetic strategy for divergent synthesis diverse types [3,4]-seven- or six-membered ring-fused 3-alkenyl-oxindoles incorporating benzazepine significant building blocks from propargyl alcohols via cascade nucleophilic substitution/site-selective hydride transfer/cyclization process unprecedentedly. In addition, variety nucleophiles, including H2O, were available controllable construction wide range conjugated alkenes, ketones, allyl encompassing natural products pharmaceutical motifs utilization 4-amine substituted isatins widespread terminal alkyne-derived alcohols. Furthermore, utility methodology mechanistic studies also well presented.

Language: Английский

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Recent Progress in Transition-Metal-Catalyzed Reductive Cross-Coupling Reactions Using Diboron Reagents as Reductants

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(23), P. 15469 - 15480

Published: Nov. 16, 2023

Transition-metal-catalyzed reductive cross-coupling reactions have been developed as one of the important tools for constructing C–C bonds. These involve direct coupling two distinct electrophiles promoted by transition metals and reductants. Notably, these methods offer advantages over conventional because they circumvent need air- moisture-sensitive organometallic reagents while being simple to operate exhibiting good compatibility with various functional groups. In recent years, diboron gained prominence reductants alongside traditional metal reductants, such Zn, Mn, Mg. This Review aims provide an insightful overview nickel/copper/iron-catalyzed using illustrate their possible reaction mechanisms.

Language: Английский

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