Visible-Light-Induced Intermolecular Dearomative Cyclization of 2-Bromo-1,3-dicarbonyl Compounds and Alkynes: Synthesis of Spiro[4.5]deca-1,6,9-trien-8-ones

Organic Letters, Journal Year: 2018, Volume and Issue: 20(18), P. 5762 - 5765

Published: Sept. 7, 2018

A visible-light-induced photocatalytic intermolecular dearomative cyclization of 2-bromo-1,3-dicarbonyl compounds and alkynes afforded biologically important spirocarbocycle structures in moderate to good yields via a 5-exo-dig radical under mild reaction conditions. 5.0 mmol scale dearomatization proceeded smoothly with 95% yield even when the catalyst loading was reduced 0.1 mol %, suggesting that this method suitable for large-scale synthesis.

Language: Английский

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Pd-Catalyzed Dearomative Three-Component Reaction of Bromoarenes with Diazo Compounds and Allylborates

ACS Catalysis, Journal Year: 2019, Volume and Issue: 9(10), P. 8991 - 8995

Published: Sept. 3, 2019

A catalytic dearomative three-component reaction of bromoarenes with TMS-diazomethane and allyl borate was developed. The key this assembling is the use a diazo compound to generate Pd-π-benzyl intermediate through Pd-carbene species. This method allowed for functionalization, using arenes as limiting reagents. Heteroaryl bromides were also applicable give dearomatized structures under conditions.

Language: Английский

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Asymmetric Allylic Alkylation of β-Ketoesters via C–N Bond Cleavage of N-Allyl-N-methylaniline Derivatives Catalyzed by a Nickel–Diphosphine System

ACS Catalysis, Journal Year: 2020, Volume and Issue: 10(10), P. 5828 - 5839

Published: April 22, 2020

Nickel complexes bearing chiral diphosphine ligands, such as (S)-Tol-MeO-BIPHEP and (S)-H8-BINAP, serve efficient catalysts for asymmetric allylic alkylation (AAA) of β-ketoesters, using amines allyl sources. The reactions proceed with high catalytic activity enantioselectivity. N-Methyl-N-phenyl were indispensable to achieve the activity, enantioselectivity, expand substrate scope 5- 7-membered whose nickel-catalyzed AAA alcohols results in low On basis kinetics a catalyst system made Ni(cod)2 (S)-Tol-MeO-BIPHEP, DFT calculations reaction pathway mediated by an isolated olefin-coordinated nickel–DPPF complex 4b, we propose mechanism where protonation nitrogen atom coordinating amine β-ketoester is key cleaving C–N bond delivering cationic π-allyl nickel(II) intermediate.

Language: Английский

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Enantioselective Formal [4 + 3] Annulations to Access Benzodiazepinones and Benzoxazepinones via NHC/Ir/Urea Catalysis

ACS Catalysis, Journal Year: 2021, Volume and Issue: 11(23), P. 14388 - 14394

Published: Nov. 15, 2021

A robust and scalable formal [4 + 3] annulation reaction for the synthesis of optically pure 1,4-benzodiazepinones 1,4-benzoxazepinones has been established by a combined catalytic system consisting chiral NHC, Ir/phosphine-olefin complex, an achiral urea, enabling asymmetric selective inhibitor mitochondrial F1F0 ATP hydrolase.

Language: Английский

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Regiodivergent catalytic asymmetric dearomative cycloaddition of bicyclic heteroaromatics

Science Advances, Journal Year: 2023, Volume and Issue: 9(13)

Published: March 31, 2023

The catalytic dearomative cycloaddition of bicyclic heteroaromatics including benzofurans and indoles provides rapid access to functionalized heterocyclic molecules. Because the inherent stereoelectronic differences, furan or pyrrole nucleus is more prone than benzene ring. Here, we realized a geometry-based differentiation approach for achieving C6-C7 C7-C7a regioselectivity. rotationally restricted σ bond at C7 position respectively placed sites in an optimal spatial orientation toward axially chiral heterodiene, thus affording two enantioenriched polycyclic compounds from single racemic heterobiaryl atropisomers. Calculation results density functional theory interpreted mechanism this parallel kinetic resolution. bioactivity dearomatized products was evaluated cancer cell lines with certain exhibiting interesting biological activities.

Language: Английский

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