Grignard Reagents as Simple Precatalysts for the Dehydrocoupling of Amines and Silanes DOI
Claire Bushey, Diego R. Javier‐Jiménez, Matthew B. Reuter

et al.

Dalton Transactions, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 1, 2024

Methyl magnesium bromide is a precatalyst for the dehydrocoupling of silanes and amines to produce aminosilane products under mild conditions. As commercially available Grignard reagent, this represents simplification over previous magnesium-containing catalysts Si-N bond formation while displaying similar activity other magnesium-based catalysts. This observation consistent with hypothesis that competitive Schlenk equilibrium can be addressed by not using an ancillary ligand. While MeMgBr lower than some reported catalysts, including precatalysts, unique selectivity was observed may allow directed synthesis products. work continues increase accessibility heterodehydrocoupling through growing family precatalysts balance selectivity.

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
NHC–Zn alkyl catalyzed cross-dehydrocoupling of amines and silanes DOI
Adimulam Harinath, Himadri Karmakar,

Devadkar Ajitaro Kisan

et al.

Organic & Biomolecular Chemistry, Journal Year: 2023, Volume and Issue: 21(20), P. 4237 - 4244

Published: Jan. 1, 2023

An N-heterocyclic carbene-zinc alkyl complex [ImDippZn(CH2CH3)2] (Im = imidazol-2-ylidene and Dipp 2,6-diisopropylphenyl) acts as a catalyst in the cross-dehydrogenative coupling (CDC) of wide range primary secondary amines hydrosilanes to yield substantial quantity corresponding aminosilanes with good chemoselectivity at room temperature. A broad substrate scope was observed during zinc-catalyzed CDC reaction. Two zinc complexes, [{ImMesZn(μ-NHPh)(NHPh)}2] (Mes mesityl) (3) [{ImDippZn(CH2CH3)(μ-H)}2] (4), were isolated structurally characterized intermediates through controlled reactions ascertain mechanism.

Language: Английский

Citations

9
On-demand hydrogen production at room temperature through silylation of alcohol-amines with no added catalysts DOI Creative Commons

S. M. Martin,

Abdelhamid Sayari

International Journal of Hydrogen Energy, Journal Year: 2025, Volume and Issue: 106, P. 662 - 671

Published: Feb. 5, 2025

Language: Английский

Citations

0
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
Efficient Cobalt-Catalyzed Coupling of Amines and Siloxanes to Prepare Ceramics and Polymers DOI
Anuja Sharma, Ren H. Bean, Timothy E. Long

et al.

ACS Sustainable Chemistry & Engineering, Journal Year: 2023, Volume and Issue: 11(30), P. 11172 - 11180

Published: July 17, 2023

The phosphine-substituted aryl diimine cobalt catalyst, (Ph2PPrADI)Co, has been found to mediate the dehydrocoupling of diamines or polyamines poly(methylhydrosiloxane) (PMHS) generate hydrogen and crosslinked solids in an atom-efficient fashion. resulting siloxane diamine polyamine networks persist presence air water at room temperature can tolerate temperatures up 1600 °C. Upon lowering catalyst loading 0.01 mol %, (Ph2PPrADI)Co was catalyze 1,3-propanediamine PMHS (m = 35) a foam with turnover frequency 157 s–1 relative consumption, highest activity ever reported for Si–N dehydrocoupling. Furthermore, upon systematically reducing number potential branch points, (Ph2PPrADI)Co-catalyzed hydride-terminated poly(dimethylsiloxane) (PDMS) yield linear polymers molecular weights 47,300 g/mol.

Language: Английский

Citations

5
Silane diamine copolymers: efficient synthesis, solvent absorption capacity, and limitations as coatings DOI
Thao T. Nguyen, Anuja Sharma, Tam Le Phuong Nguyen

et al.

Green Chemistry, Journal Year: 2024, Volume and Issue: 26(9), P. 5284 - 5292

Published: Jan. 1, 2024

Turnover frequencies of up to 300 s −1 have been achieved for the Mn-based dehydrocoupling silanes and diamines yield crosslinked networks that absorb organic solvents afford coatings.

Language: Английский

Citations

1
Manganese Catalysed Dehydrocoupling of Silanes and Siloxanes with Ammonia to Prepare Oligosilazanes and Polysiloxazanes DOI
G. MEHTA, Thao T. Nguyen, Marco Flores

et al.

Dalton Transactions, Journal Year: 2024, Volume and Issue: 53(34), P. 14272 - 14277

Published: Jan. 1, 2024

The manganese-catalysed dehydrocoupling of ammonia to phenylsilane affords an oligosilazane that can be applied as a coating.

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 Garcı́a-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