Nickel-Catalyzed Migratory Cross-Coupling Reactions: New Opportunities for Selective C–H Functionalization

Accounts of Chemical Research, Journal Year: 2023, Volume and Issue: 56(23), P. 3475 - 3491

Published: Nov. 16, 2023

ConspectusMigratory cross-coupling via metal migration is a process of significant academic and industrial interest. It provides an attractive alternative for the selective installation functional group at remote C-H positions from simple precursors, thus enabling direct synthesis challenging structures not accessible with traditional cross-coupling. In particular, merger 1,n-Ni/H shift nickel, Ni-catalyzed migratory functionalization precursors has undergone particularly intense development emerged as valuable field research in past few years. This Account will outline recent progress made this arena terms migration-functionalization modes, diverse functionalizations, strategies regio- stereocontrol. Mechanistic studies synthetic applications are also discussed.In detail, we systematically categorize our work into two parts based on modes. first part, platform created sp3 alkenes or alkyl halides iterative 1,2-Ni/H shift-selective The key reactive Ni(II)H species chain-walking could be generated situ either polarity-reversed fashion relying stoichiometric reductants (X-Ni(II)-H) redox-neutral participation nucleophilic coupling partners (FG-Ni(II)-H). One advantage associated NiH system use relatively stable, abundant, safe olefin surrogates instead sensitive organometallics required reactions. Another that including carbonation more amination thiolation smoothly achieved suitable electrophiles their precursors. Finally, to address multifaceted selectivity reactivity issues asymmetric reactions, have developed feasible ligand relay catalytic strategy. dynamic exchange process, one promotes rapid while other highly stereoselective coupling. innovative strategy overcomes formidable challenge stemming difficulty designing single efficiently promote both steps second new sp2 1,4-Ni/H been reported. Starting readily available aryl vinyl partners, situ-generated aryl- vinylnickel(II) undergo reversible along backbone, subsequent various would allow access 1,4-migratory products. success was discovery appropriate A vinyl-to-aryl successfully enables modular ipso/ortho difunctionalization aryl-to-vinyl functionalized trisubstituted alkenes.We hope inspire broad interest future We strongly believe continued efforts fascinating overcome many remaining challenges, cutting-edge ligand/catalyst design enhance selectivity, conceptually modes additional transformations, in-depth mechanistic rational reaction design.

Language: Английский

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Functionalization of Olefinic C−H Bonds by an Aryl‐to‐Vinyl 1,4‐Nickel Migration/Reductive Coupling Sequence

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(28)

Published: May 6, 2023

An attractive approach to selective functionalization of remote C-H bonds is a metal/hydride shift/cross-coupling reaction sequence. Complimentary the heavily exploited 1,2-nickel/hydride shift along an sp3 chain, chain-walking process, 1,4-nickel/hydride sp2 chain more complex. Here we report unprecedented aryl-to-vinyl reaction, in which migratory alkenylnickel species generated situ selectively trapped by one various coupling partners, such as isocyanates, alkyl bromides, aryl chlorides or alkynyl allowing regio- and stereoselective access trisubstituted alkenes. In contrast well-reported ipso-aryl reactions, this strategy provides alkenyl functionalized products with good yield excellent chemo-, E/Z-selectivity.

Language: Английский

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Alkyne Insertion Enabled Vinyl to Acyl 1,5‐Palladium Migration: Rapid Access to Substituted 5‐Membered‐Dihydrobenzofurans and Indolines

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(18)

Published: Feb. 21, 2023

"Through space" palladium/hydrogen shift is an efficient strategy to achieve selective functionalization of a specific remote C-H bond. Compared with relatively extensive exploited 1,4-palladium migration process, the relevant 1,5-Pd/H was far less investigated. We herein report novel pattern between vinyl and acyl group. Through pattern, rapid access 5-membered-dihydrobenzofuran indoline derivatives has been achieved. Further studies have unveiled unprecedented trifunctionalization (vinylation, alkynylation amination) phenyl ring through 1,5-palladium relayed decarbonylative Catellani type reaction. A series mechanistic investigations DFT calculations provided insights into reaction pathway. Notably, it that in our case prefers stepwise mechanism involving PdIV intermediate.

Language: Английский

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Aryl‐to‐Vinyl 1,4‐Nickel Migration/Reductive Cross‐Coupling Reaction for the Stereoselective Synthesis of Multisubstituted Olefins

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(28)

Published: May 5, 2023

The aryl-to-vinyl nickel 1,4-migration (1,4-Ni migration) reaction has been reported for the first time. generated alkenyl Ni species undergo a reductive coupling with unactivated brominated alkanes affording series of trisubstituted olefins. This tandem exhibits mild conditions, broad substrate scope, high regioselectivity, and excellent Z/E stereoselectivity. A controlled experiments have shown that critical 1,4-Ni migration process is reversible. In addition, intermediates obtained after are highly stereoselective do not isomerization. trace isomerization products caused by instability product.

Language: Английский

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1,3-diene-based AIEgens: Stereoselective synthesis and applications

iScience, Journal Year: 2024, Volume and Issue: 27(3), P. 109223 - 109223

Published: Feb. 15, 2024

SummaryIn recent years, significant advancements have been made in the synthesis and application of 1,3-dienes. This specific structural motif has garnered attention from researchers materials science biology due to its unique aggregation-induced emission (AIE) properties extensive conjugation systems. The luminescent characteristics these compounds are notably influenced by geometry two double bonds. Therefore, it is essential consolidate stereoselective synthetic strategies for comprehensive review seeks elucidate diverse techniques employed attain stereo-control 1,3-diene-based AIE luminogens (AIEgens). Particular emphasis placed on comprehending determinants stereoselectivity exploring array substrates amenable methods. Furthermore, underscores exhibited their utility organic light-emitting diodes (OLEDs), stimuli-responsive materials, sensors, bioimaging, photodynamic therapy (PDT).Graphical abstract

Language: Английский

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Palladium-Catalyzed Skeletal Rearrangement of Cyclobutanones via C–H and C–C Bond Cleavage

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(4), P. 2234 - 2239

Published: Jan. 27, 2023

The palladium-catalyzed skeletal rearrangement of 3-arylcyclobutanones into 1-indanones is reported. A Pd(0)/IMes catalyst allows for the cleavage C(carbonyl)–C(sp3) and C(sp2)–H bonds to result in rearrangement, neither an extra reactive functional group nor a directing required promote reaction. Deuterium-labeling experiments indicate that C–C bond initially activated subsequent C–H activation involved rate-determining step.

Language: Английский

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Trisubstituted alkenes featuring aryl groups: stereoselective synthetic strategies and applications

Science China Chemistry, Journal Year: 2023, Volume and Issue: 66(5), P. 1261 - 1287

Published: April 17, 2023

Language: Английский

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Divergent Synthesis of Enantioenriched Silicon‐Stereogenic Benzyl−, Vinyl− and Borylsilanes via Asymmetric Aryl to Alkyl 1,5‐Palladium Migration

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(36)

Published: July 30, 2024

Functionalization of Si-bound methyl group provides an efficient access to diverse organosilanes. However, the asymmetric construction silicon-stereogenic architectures by functionalization has not yet been described despite recent significant progress in producing chiral silicon. Herein, we disclosed enantioselective silylmethyl involving aryl alkyl 1,5-palladium migration naphthalenes possessing enantioenriched stereogenic silicon center, which are inaccessible before. It is worthy note that realization induction at step metal itself remains challenging. Our study constitutes first reaction. The key success discovery and fine-tuning different substituents α,α,α,α-tetraaryl-1,3-dioxolane-4,5-dimethanol (TADDOL)-based phosphoramidites, ensure enantioselectivity desired reactivity.

Language: Английский

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Highly Stereoselective Synthesis of 1,3‐Enynes via Aryl to Vinyl 1,4‐Palladium Migration/Sonogashira Coupling Sequence

ChemCatChem, Journal Year: 2024, Volume and Issue: 16(16)

Published: April 12, 2024

Abstract Alkynylation of alkenyl bromoarenes via aryl to vinyl 1,4‐palladium migration/copper‐free Sonogashira coupling sequence has been developed. This approach provides a facile methodology for the highly stereoselective synthesis multi‐substituted 1,3‐enynes in good excellent yields and regioselectivities.

Language: Английский

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Site-Selective Carbonylative Cyclization with Two Allylic C–H Bonds Enabled by Radical Differentiation

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(29), P. 19635 - 19642

Published: July 9, 2024

Controlling the site-selectivity of C-H functionalization is significant importance and a formidable undertaking in synthetic organic chemistry, motivating continuing development efficient sustainable technologies for activating bonds. However, methods that control double are rare. We herein report conceptually new method to achieve highly site-selective by implementing radical single-out strategy. Leveraging steric hindrance-sensitive CO-insertion as differentiation process, stereoselective carbonylative formal [2 + 2] cycloaddition imines alkenes sequential allylic bond activation was established without special complicated HAT-reagents. This reaction compatible with wide range diverse skeletons deliver β-lactams medicinal interest.

Language: Английский

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