Catalytic synthesis of β-lactam derivatives by carbonylative cycloaddition of acylsilanes with imines via a palladium Fischer-carbene intermediate

Nature Catalysis, Год журнала: 2024, Номер 7(2), С. 132 - 138

Опубликована: Янв. 15, 2024

Abstract Fischer-type carbene complexes are characterized by the presence of a π -donating group, such as an alkoxy group on carbon. Despite notable progress that has been made in synthetic methods involve use complexes, stoichiometric amounts still required for reactions and catalytic variants remain elusive. This limitation primarily stems from lack suitable precursors, which is sharp contrast to fact bearing electron-withdrawing can be readily generated corresponding diazo esters. Here we report acylsilanes function precursor Fischer-carbene complex action palladium catalyst. system used carbonylative cycloaddition with imines form densely substituted β-lactam derivatives. A key siloxycarbene–palladium intermediate was isolated successfully X-ray crystallography.

Язык: Английский

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The role of silicon in drug discovery: a review

RSC Medicinal Chemistry, Год журнала: 2024, Номер 15(10), С. 3286 - 3344

Опубликована: Янв. 1, 2024

This review aims to highlight the role of silicon in drug discovery.

Язык: Английский

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Silylarylation of Alkenes via meta-Selective C–H Activation of Arenes under Ruthenium/Iron Cooperative Catalysis: Mechanistic Insights from Combined Experimental and Computational Studies

ACS Catalysis, Год журнала: 2024, Номер 14(7), С. 4510 - 4522

Опубликована: Март 12, 2024

Organosilicons are privileged skeletons in the domains of pharmaceutical chemistry, organic synthesis, and materials science. Hence, investigating catalytic techniques for synthesis organosilicon compounds has received a great deal emphasis. Carbosilylation alkenes is an efficient technique to introduce diverse molecular architectures containing silicon into chemical space. However, organohalides pseudohalides prerequisites most existing carbosilylation protocols. On other hand, utilization C–H activation been sowing seeds successful development intricate scaffolds. In this regard, synthetic accessibility complexed derivatives by through meta-C–H approach remained intangible. Herein, we present three-component strategy arylsilylation olefins with (het)arenes silanes integrating iron-catalyzed silyl radical generation, coupled intrinsic reactivity alkene, ruthenium-catalyzed functionalization (het)arene, leading targeted cross-coupled carbosilylated product. addition, theoretical investigations state-of-the-art dispersion corrected density functional theory at B3PW91-D3/Def2TZVP/CPCM(PhCF3) shed intriguing insights on selectivity probable mechanistic pathway underexplored cooperative 3d/4d transition metal catalysis, such as formation its addition alkene catalyzed iron, followed meta-selective ruthenium bound arene, furnishing C4 substituted (het)arene functionalized compounds.

Язык: Английский

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Asymmetric Trapping of Siloxyketenes In Situ Generated from [1,3]-Silyl Migration of α-Ketoacylsilanes: A Visible-Light-Driven Palladium-Catalyzed [4 + 2] Cycloaddition

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 5796 - 5805

Опубликована: Март 25, 2025

The transition metal-catalyzed asymmetric [n + 2] cycloaddition reaction with oxy-substituted ketene intermediates remains a synthetic challenge due to the limited availability of suitable precursors. Herein, we report visible-light-driven, palladium-catalyzed [4 vinyl benzoxazinanones siloxyketene intermediates, generating structurally diverse chiral quinolinone derivatives satisfactory diastereo- and enantioselectivities. transient generation siloxyketenes from α-ketoacylsilylanes through visible-light-induced Brook rearrangement is important for success present cycloaddition. 13C-labeling experiments reveal pathway involving [1,3]-silyl migration process. side arm effects BOX ligand silyl steric hindrance α-ketoacylsilanes play crucial roles in stereoselectivity control, theoretical calculations provide insights into stereochemical outcome reaction.

Язык: Английский

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Palladium-Catalyzed Addition of Trifluoroacetylsilanes to Alkenes and Allenes via the Cleavage of C–Si Bonds

Organic Letters, Год журнала: 2024, Номер 26(10), С. 2141 - 2145

Опубликована: Март 5, 2024

The palladium-catalyzed addition of trifluoroacetylsilanes to alkenes and allenes via the cleavage C–Si bonds is reported. When are used, cyclopropanation occurs afford cyclopropane derivatives bearing CF3 siloxy groups with a high degree stereoselectivity. silylacylation form alkenylsilane trifluoroacetyl group at allylic position complete regioselectivity. Both reactions allow for highly atom-economical access densely functionalized fluorinated organosilane using simple building blocks.

Язык: Английский

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Light-Promoted Arylsilylation of Alkenes with Hydrosilanes

Organic Letters, Год журнала: 2022, Номер 24(39), С. 7145 - 7150

Опубликована: Сен. 22, 2022

Herein, we report light-promoted photo/hydrogen atom transfer dual catalysis for arylsilylation of alkenes via the radical-radical cross-coupling with diverse hydrosilanes, which provides a simple and efficient method to prepare various organosilicon compounds wide range substrate scope good functional group tolerance under transition-metal- chemical-oxidant-free conditions. Furthermore, can also proceed possible electron donor-acceptor complex exogenous photocatalyst-free

Язык: Английский

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Interplay of Ligand-Controlled Reaction Pathways: DFT Analysis of Mechanisms and Selectivities in Pd-Catalyzed Semireduction of Allenamides

Molecular Catalysis, Год журнала: 2024, Номер 560, С. 114126 - 114126

Опубликована: Апрель 12, 2024

Язык: Английский

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Emerging applications of acylsilanes in organic synthesis and beyond

Organic Chemistry Frontiers, Год журнала: 2023, Номер 10(5), С. 1316 - 1321

Опубликована: Янв. 1, 2023

The last two years have witnessed unprecedentedly wide applications of acylsilanes in many fields well beyond pure organic synthesis. This highlight covers selected representative examples and focuses on their possible the future.

Язык: Английский

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Palladium-catalyzed addition of acylsilanes across alkynes via the activation of a C–Si bond

Chemical Science, Год журнала: 2023, Номер 14(10), С. 2706 - 2712

Опубликована: Янв. 1, 2023

Palladium-catalyzed addition of a C–Si bond in acylsilanes across the triple bonds an alkyne bearing carbonyl group at one terminal is reported.

Язык: Английский

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Acylsilanes as Weakly Coordinating Directing Groups for Metal-Catalyzed C–H Functionalization

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 6881 - 6894

Опубликована: Апрель 14, 2025

Язык: Английский

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