Catalytic Asymmetric Cascade Dearomatization of Indoles via a Photoinduced Pd‐Catalyzed 1,2‐Bisfunctionalization of Butadienes

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(26)

Published: April 20, 2024

Photoinduced Pd-catalyzed bisfunctionalization of butadienes with a readily available organic halide and nucleophile represents an emerging attractive method to assemble versatile alkenes bearing various functional groups at the allylic position. However, enantiocontrol and/or diastereocontrol in C-C or C-X bond-formation step have not been solved due open-shell process. Herein, we present cascade asymmetric dearomatization reaction indoles via photoexcited 1,2-biscarbonfunctionalization 1,3-butadienes, wherein control on both electrophile part is achieved for first time photoinduced butadienes. This delivers structurally novel chiral spiroindolenines two contiguous stereogenic centers high diastereomeric ratios (up >20 : 1 dr) good excellent enantiomeric 97 3 er). Experimental computational studies mechanism confirmed radical pathway involving excited-state palladium catalysis. The alignment non-covalent interactions between substrate catalyst were found be essential stereocontrol.

Language: Английский

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Photoinduced Pd-Catalyzed Formal Asymmetric Allylic Substitution of Piperidine Scaffolds

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 4384 - 4393

Published: Feb. 26, 2025

Language: Английский

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Enantioselective Synthesis of Allylic Sulfones via Rhodium-Catalyzed Direct Hydrosulfonylation of Allenes and Alkynes

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(25), P. 16996 - 17002

Published: June 14, 2024

A highly regio- and enantioselective hydrosulfonylation using commercially available sodium sulfinates is reported, providing the first direct asymmetric rhodium-catalyzed of allenes/alkynes to synthesize chiral allylic sulfones. Ligand screening studies demonstrated indispensable role C1-symmetric P,N-ligand (Rax,S,S)-StackPhim for achieving both high regioselecitivity (>20:1) enantioselectivity (up 97% ee). Notably, operationally simple method mild conditions allow rapid preparation sulfones with a wide scope functional groups. Moreover, use tert-butyldimethylsilyloxymethanesulfinate enables collective synthesis various sulfone derivatives after transformations protected hydroxymethyl product.

Language: Английский

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Photoinduced Pd‐Catalyzed Direct Sulfonylation of Allylic C–H Bonds

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 64(1)

Published: Sept. 17, 2024

Allylic sulfones are valuable motifs due to their medicinal and biological significance versatile chemical reactivities. While direct allylic C-H sulfonylation represents a straightforward desirable approach, these methods primarily restricted terminal alkenes, leaving the engagement of internal counterparts formidable challenge. Herein we report photocatalytic approach that accommodates both cyclic acyclic alkenes with diverse substitution patterns electronic properties. Importantly, obtained can be readily diversified into wide range products, thus enabling formal alkene transposition all-carbon quaternary center formation through sequential functionalization.

Language: Английский

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Palladium-Catalyzed Decarboxylative Allylic Sulfonylation of Vinyloxazolidine-2,4-diones: Synthesis of γ-Sulfonyl-α,β-unsaturated Amides

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 10, 2025

A palladium-catalyzed decarboxylative allylic sulfonylation reaction of vinyloxazolidine-2,4-diones with inexpensive and readily available sodium sulfinates as reagents has been developed. Under the catalysis Pd(PPh3)4, a wide range γ-sulfonyl-α,β-unsaturated amides can be synthesized in good to excellent yields. The developed protocol is characterized by exclusive regioselectivity, mild conditions, broad substrate scope, functional group tolerance, suitable for gram-scale synthesis.

Language: Английский

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Copper-Catalyzed Regio- and Enantioselective Protoboration of Allenyl Sulfones to Access Chiral Allylic Sulfones

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 14, 2025

An efficient method for copper-catalyzed asymmetric protoboration of allenyl sulfones with bis(pinacolato)diboron was developed, providing chiral allylic high efficiency and excellent enantioselectivity. Notably, the directing effect sulfone group plays a pivotal role in achieving both regioselectivity

Language: Английский

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An Overview of Recent Advances in Enantioselective Multicomponent Reactions

Journal of Molecular Structure, Journal Year: 2025, Volume and Issue: unknown, P. 141768 - 141768

Published: Feb. 1, 2025

Language: Английский

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Illuminating Palladium Catalysis

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

Published: Feb. 26, 2025

ConspectusThe past decade has witnessed significant advancements of visible-light-induced photocatalysis, establishing it as a powerful and versatile tool in organic synthesis. The major focus this field centered on the development methodologies that either rely solely photocatalysts or combine photocatalysis with other catalytic methods, such transition metal catalysis, to address broader more diverse array transformations. Within rapidly evolving area, subfield we refer garnered attention due its growing impact mechanistic uniqueness. A distinguishing feature is dual functionality single complex, which not only acts photocatalyst initiate photochemical processes but also functions traditional catalyst, facilitating key bond-breaking bond-forming events. As such, an exogenous required photocatalysis. However, implications harnessing both excited- ground-state reactivities complex can extend beyond simplification. One most compelling aspects area photoexcited complexes exhibit unique inaccessible through conventional thermal photocatalytic approaches. These distinct be leveraged accomplish novel transformations by engaging entirely different substrate pool unlocking new known substrates.In 2016, our group pioneered use phosphine-ligated palladium catalysts upon visible-light irradiation engage substrates radical reactions. In initial discovery, showed photoexcitation redirect well-established oxidative addition Pd(0) into aryl iodides toward unprecedented process, generating hybrid Pd(I) species. We subsequently extended strategy formation alkyl radicals from halides. reactive intermediates have been harnessed wide variety transformations, including desaturation, Heck reactions, alkene difunctionalization cascades, among others.Seeking further expand avenue, achieved first example asymmetric context allylic C–H amination, where catalyst now plays triple duty additionally controlling stereochemical outcome reaction. parallel reaction established diazo compounds, strained molecules, electron-deficient alkenes serve precursors halides redox-active esters. Notably, engagement made possible photoinduced hydricity enhancement Pd–H species, representing mode reactivity.This Account presents discovery organized type explored. Given rapid progress field, anticipate will provide readers guiding principles inspiration for designing developing efficient

Language: Английский

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Access to 5- to 14-Membered N-Heterocycles by Alkylamination of 1,3-Dienes via Palladium Catalysis

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: March 12, 2025

Medium-sized rings show great potential in medicinal chemistry but are difficult to achieve via direct cyclization reaction. We herein report a versatile and mild photocatalytic approach for synthesis of medium- large-sized vinyl N-heterocycles by radical-mediated sulfonamides with pendant 1,3-dienes. The reaction involves the generation radicals from alkyl halides π-allylpalladium species. This method could serve as platform construction Pd catalysis.

Language: Английский

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Radical-mediated sulfonylation relay of alkyl alkynes/alkenes and electron-deficient alkenes to access vinyl and alkyl sulfones

Organic Chemistry Frontiers, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

A radical-mediated sulfonylation relay of alkyl alkynes/alkenes with electron-deficient alkenes using Na 2 S O 4 as a linker is developed to synthesize highly selective ( Z )-vinyl and sulfones under metal-free catalyzed system.

Language: Английский

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