Group I Alkoxides and Amylates as Highly Efficient Silicon–Nitrogen Heterodehydrocoupling Precatalysts for the Synthesis of Aminosilanes DOI Creative Commons
Matthew B. Reuter, Diego R. Javier‐Jiménez, Claire Bushey

et al.

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 29(66)

Published: Sept. 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.

Language: Английский

Synthesis of Alkynylsilanes: A Review of the State of the Art DOI
Krzysztof Kuciński

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(11), P. 2382 - 2431

Published: April 12, 2024

Abstract This contribution offers a comprehensive overview of methods for forging sp C−Si bonds. Over time, alkynylsilanes (silylacetylenes), once considered mere byproducts hydrosilylation processes, have become essential building blocks in organic synthesis. literature review traces the evolution their synthesis, from traditional methodologies relying on organolithium and organomagnesium compounds to more advanced cross‐coupling reactions involving hydro‐ carbosilanes. Focused primarily past 25 years (2000–2024), it also extensively references significant historical breakthroughs. By analyzing synthetic methodologies, not only survey current state knowledge but identifies areas improvement. Furthermore, emphasize importance 1‐alkynylsilanes (1‐silyl‐1‐alkynes), selected applications these are highlighted, confirming potential

Language: Английский

Citations

6
Carboxylate-Catalyzed C-Silylation of Terminal Alkynes DOI Creative Commons
Anton Bannykh, Petri M. Pihko

Organic Letters, Journal Year: 2024, Volume and Issue: 26(10), P. 1991 - 1995

Published: March 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.

Language: Английский

Citations

4
Recent progress of organosilicon compound: synthesis and applications DOI
Hoda Mollabagher, Mohammad M. Mojtahedi, Seyed Amir Hossein Seyed Mousavi

et al.

Journal of the Iranian Chemical Society, Journal Year: 2024, Volume and Issue: 21(7), P. 1795 - 1816

Published: June 28, 2024

Language: Английский

Citations

4
Cobalt-catalyzed synthesis of silyl ethers via cross-dehydrogenative coupling between alcohols and hydrosilanes DOI Creative Commons
Ewelina Szafoni, Krzysztof Kuciński, Grzegorz Hreczycho

et al.

Green Chemistry Letters and Reviews, Journal Year: 2022, Volume and Issue: 15(3), P. 757 - 764

Published: July 3, 2022

Various commercially available primary and secondary hydrosilanes were exploited for versatile direct dehydrocoupling with alcohols phenols through cobalt catalysis. The protocol enables efficient Si–O bond formation a host of O–nucleophiles silanes (27 examples, 67–91% yield), precatalyst loadings 0.5–2 mol%. Beyond enabling practical greener approach to silyl ethers, this type pincer-supported catalysis provides blueprint the development broad range reactions leading synthetically relevant organometalloids. Moreover, use as substrates activators permits inexpensive easily accessible Earth-abundant metal complexes avoids presence additional activators.

Language: Английский

Citations

16
Access to germasiloxanes and alkynylgermanes mediated by earth-abundant species DOI Creative Commons
Hanna Stachowiak, Krzysztof Kuciński, Konstancja Broniarz

et al.

Scientific Reports, Journal Year: 2023, Volume and Issue: 13(1)

Published: April 6, 2023

The reactions between silanols or terminal acetylenes with alkynylgermanes have been accomplished using potassium bis(trimethylsilyl)amide as the catalyst. This strategy has provided an entry point into various organogermanes including germasiloxanes and alkynylgermanes. Remarkably, not only KHMDS but also simple bases such KOH can serve efficient catalysts in this process.

Language: Английский

Citations

9
Diverse Reactions of α‐Diimine‐Ligated MgI−MgI‐Bonded Compound with Carbodiimides DOI
Yang Li, Yao Qu,

Juju Wang

et al.

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 29(44)

Published: May 25, 2023

The α-diimine-ligated dimagnesium(I) compound [K(thf)3 ]2 [LMg-MgL] (1, L=[(2,6-iPr2 C6 H3 )NC(Me)]22- ) displays diverse reactivities toward carbodiimides (RN=C=NR) with different R substituents. In the reaction of 1 Me3 SiNCNSiMe3 , one easily leaving trimethylsilyl groups is lost to yield SiNCN- moiety that either bridges two MgII centers (2) or terminally coordinated (3). contrast, similarly bulky tBuNCNtBu, carbodiimide inserts into Mg-Mg bond accompanying C-H activation a ligand solvent (products 4 and 5). case dicyclohexyl diisopropyl carbodiimide, reductive C-C coupling RNCNR molecules occurs form [C2 (NR)4 ]2- diamido moiety, which Mg centers, giving complexes [{K(dme)2 }2 LMg(μ-{C2 })MgL] (6, R=Cy; 7, R=iPr) [L⋅- Mg(μ-{C2 })MgL⋅- ] (8). Most interestingly, upon treating SiC≡CSiMe3 acetylide complex [K(dme)][LMg(C≡CSiMe3 )(dme)] (9) was prepared, undergoes rare "double insertion" CyNCNCy afford [K(solv)][K(dme)2 LMg(NCy)2 C-C≡C-C(NCy)2 MgL] (10) containing an acetylenediide-coupled bis(amidinate) atoms.

Language: Английский

Citations

7
Cobalt‐Driven Cross‐Dehydrocoupling of Silanes and Amines for Silylamine Synthesis DOI
Ewelina Szafoni, Krzysztof Kuciński, Grzegorz Hreczycho

et al.

ChemCatChem, Journal Year: 2024, Volume and Issue: 16(15)

Published: May 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.

Language: Английский

Citations

2
Streamlining Si-O Bond Formation Through Cobalt-Catalyzed Dehydrocoupling DOI
Ewelina Szafoni, Dariusz Lewandowski, Marcin Gruszczyński

et al.

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(78), P. 10886 - 10889

Published: Jan. 1, 2024

Herein we report a strategy for the synthesis of organosilicons, including siloxanes, silyl ethers, and aminosilanes,

Language: Английский

Citations

2
Facile Synthesis of Ultra-Small Silver Nanoparticles Stabilized on Carbon Nanospheres for the Etherification of Silanes DOI Creative Commons
Minghui Liu, He Huang,

Changwei An

et al.

Nanomaterials, Journal Year: 2024, Volume and Issue: 14(13), P. 1095 - 1095

Published: June 26, 2024

The dehydrocoupling reaction between alcohols and hydrosilanes is considered to be one of the most atom-economical ways produce Si–O coupling compounds because its byproduct only hydrogen (H2), which make it extremely environmentally friendly. In past decades, various kinds homogeneous catalysts for hydrosilanes, such as transition metal complexes, alkaline earth metals, alkali noble have been reported their good activity selectivity. Nevertheless, practical applications these still remain unsatisfactory, mainly restricted by environmental impact non-reusability. A facile recyclable heterogeneous catalyst, ultra-small Ag nanoparticles supported on porous carbon (Ag/C) etherification silanes, has developed. It high catalytic reaction, apparent activation energy about 30 kJ/mol. dispersed in catalyst through carrier C an enrichment effect all reactants, makes reactants reach adsorption saturation state surface nanoparticles, thus accelerating process verifying that kinetics indicate a zero-grade reaction.

Language: Английский

Citations

1
Cross-Dehydrogenative Coupling of Secondary Amines with Silanes Catalyzed by Agostic Iridium-NSi Species DOI Creative Commons
Marina Padilla, María Batuecas, Pilar García‐Orduña

et al.

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 64(1), P. 255 - 267

Published: Dec. 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.

Language: Английский

Citations

1