Carboxylate-Catalyzed C-Silylation of Terminal Alkynes

Organic Letters, Год журнала: 2024, Номер 26(10), С. 1991 - 1995

Опубликована: Март 1, 2024

A carboxylate-catalyzed, metal-free C-silylation protocol for terminal alkynes is reported using a quaternary ammonium pivalate as the catalyst and commercially available N,O-bis(silyl)acetamides silylating agents. The reaction proceeds under mild conditions, tolerates range of functionalities, enables concomitant O- or N-silylation acidic OH NH groups. Hammett ρ value +1.4 ± 0.1 obtained para-substituted 2-arylalkynes consistent with proposed catalytic cycle involving turnover-determining deprotonation step.

Язык: Английский

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On-demand hydrogen production at room temperature through silylation of alcohol-amines with no added catalysts

International Journal of Hydrogen Energy, Год журнала: 2025, Номер 106, С. 662 - 671

Опубликована: Фев. 5, 2025

Язык: Английский

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Cobalt‐Driven Cross‐Dehydrocoupling of Silanes and Amines for Silylamine Synthesis

ChemCatChem, Год журнала: 2024, Номер 16(15)

Опубликована: Май 8, 2024

Abstract Cobalt complexes featuring triazine‐based PNP ligands have proven to be exceptionally active and chemoselective pre‐catalysts in facilitating the dehydrogenative coupling between silanes amines, leading synthesis of diverse aminosilanes. Notably, even challenging substrates exhibited high reactivity. The catalyst‘s unique feature avoiding with tertiary enhances process chemoselectivity. It facilitates a more precise silylamines possessing SiH 2 −N SiH−N motifs, overcoming challenges associated broader reactivity seen previous systems. In terms its remarkable chemoselectivity, it is also noteworthy that catalytic system exhibits both versatility efficacy converting untouched double triple carbon‐carbon bonds. This accomplishment particularly significant, given brought about by activity commonly employed catalysts competitive hydrosilylation process.

Язык: Английский

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Tri-coordinated zinc alkyl complexes with N^S/Se coordination of imino-phosphanamidinate chalcogenide ligands as precursors for efficient hydroboration of nitriles and esters

Dalton Transactions, Год журнала: 2024, Номер 53(25), С. 10592 - 10602

Опубликована: Янв. 1, 2024

A series of tri-coordinated zinc alkyl complexes with imino-phosphanamidinate chalcogenide ligands were prepared and utilized as catalysts in the hydroboration reaction nitriles esters to obtain N , -diborylamines boronate esters.

Язык: Английский

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Cross-Dehydrogenative Coupling of Secondary Amines with Silanes Catalyzed by Agostic Iridium-NSi Species

Inorganic Chemistry, Год журнала: 2024, Номер 64(1), С. 255 - 267

Опубликована: Дек. 23, 2024

An active catalytic system for the cross-dehydrogenative coupling (CDC) of a wide range secondary amines with silanes is reported. The iridium(III) derivatives [Ir(H)(X)(κ2-NSiDMQ)(L)] (NSiDMQ = {4,8-dimethylquinoline-2-yloxy}dimethylsilyl; L coe, X Cl, 2; OTf, 3; PCy3, 4; 5), which are stabilized by weak yet noticeable Ir···H–C agostic interaction between iridium and one C–H bonds 8-Me substituent NSiDMQ ligand, have been prepared fully characterized. These species proven to be effective catalysts CDC hydrosilanes. best performance (TOF1/2 79,300 h–1) was obtained using 5 (0.25 mol %), N-methylaniline, HSiMe2Ph. activity [Ir(H)(OTf)(κ2-NSiQ)(PCy3)] (10, NSiQ {quinoline-2-yloxy}dimethylsilyl) [Ir(H)(OTf)(κ2-NSiMQ)(PCy3)] (11, NSiMQ {4-methylquinoline-2-yloxy}dimethylsilyl), related but lacking substituent, markedly lower than that found 5. This fact highlights crucial role ligand in enhancing these complexes.

Язык: Английский

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Commercially available organolithium compounds as effective, simple precatalysts for silicon–nitrogen heterodehydrocoupling

Dalton Transactions, Год журнала: 2023, Номер 52(38), С. 13497 - 13506

Опубликована: Янв. 1, 2023

A family of commercially available organolithium compounds were found to effectively catalyze the heterodehydrocoupling silanes and amines under ambient conditions.

Язык: Английский

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Group I Alkoxides and Amylates as Highly Efficient Silicon–Nitrogen Heterodehydrocoupling Precatalysts for the Synthesis of Aminosilanes

Chemistry - A European Journal, Год журнала: 2023, Номер 29(66)

Опубликована: Сен. 20, 2023

Group I alkoxides are highly active precatalysts in the heterodehydrocoupling of silanes and amines to afford aminosilane products. The broadly soluble commercially available KOt Amyl was utilized as benchmark precatalyst for this transformation. Challenging substrates such anilines were found readily couple primary, secondary, tertiary high conversions (>90 %) after only 2 h at 40 °C. Traditionally challenging Ph3 SiH also easily coupled simple primary secondary under mild conditions, with reactivity that rivals many rare earth transition-metal catalysts Preliminary evidence suggests formation hypercoordinated intermediates, but radicals detected catalytic indicating a mechanism is Si-N bond formation.

Язык: Английский

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Efficient cyanosilylation of carbonyls using a well-defined dimeric sodium complex

Journal of Organometallic Chemistry, Год журнала: 2024, Номер 1020, С. 123350 - 123350

Опубликована: Сен. 2, 2024

Язык: Английский

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An Aniline-Bridged Bis(pyrazolyl)alkane Ligand for Dizinc-Catalysed Ring-Opening Polymerization

Dalton Transactions, Год журнала: 2024, Номер unknown

Опубликована: Янв. 1, 2024

We report the first binucleating aniline ligand (1), and compare its dizinc complexes to analogous phenolate both structurally in ring-opening polymerizaion catalysis.

Язык: Английский

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