Catalytic Generation of Superbasic Carbanions DOI Open Access
Ozora Sasamoto

Journal of Synthetic Organic Chemistry Japan, Journal Year: 2024, Volume and Issue: 82(8), P. 825 - 826

Published: Aug. 1, 2024

Superbasic carbanions such as phenyl anion and t-butyl have been commonly utilized in organic synthesis, typically prepared using stoichiometric organometallic reagents (e.g., alkyllithium, Grignard reagents). The activation of organosilicon compounds with Lewis base represented by Hosomi-Sakurai allylation is another attractive way to generate reactive relatively mild conditions. While this reaction system has extensively investigated so far, its extension superbasic remains unexplored. This short review describes the recent advancements catalytic methodologies for production from compounds.

Language: Английский

Tetravalent Cerium Alkyl and Benzyl Complexes DOI Creative Commons
Haruko Tateyama, Andrew C. Boggiano, Can Liao

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(15), P. 10268 - 10273

Published: April 2, 2024

High-valent cerium complexes of alkyl and benzyl ligands are unprecedented due to the incompatibility typically highly oxidizing Ce4+ ion reducing or ligand. Herein we report synthesis isolation first tetravalent supported by tri-tert-butyl imidophosphorane ligand, [NP(tBu)3]1–. The monoiodide complex, [Ce4+I(NP(tert-butyl)3)3] (1-CeI), serves as a precursor complexes, [Ce4+(Npt)(NP(tert-butyl)3)3] (2-CeNpt) (Npt = neopentyl, CH2C(CH3)3) [Ce4+(Bn)(NP(tert-butyl)3)3] (2-CeBn) (Bn benzyl, CH2Ph). bonding structure these characterized single-crystal XRD, NMR UV–vis–NIR spectroscopy, cyclic voltammetry, DFT studies.

Language: Английский

Citations

8
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
C–H functionalization through benzylic deprotonation with π-coordination or cation–π-interactions DOI
Hui Zhu, Yu Wu, Jianyou Mao

et al.

Chemical Society Reviews, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Transition-metals bind arene π-systems, removing e − density and acidifying benzylic C–H’s. Main group metals achieve this via cation–π interactions. Both interactions enable catalytic base-promoted selective C–H functionalization.

Language: Английский

Citations

0
Catalytic Alkoxysilylation of C–H bonds with tert-Butyl-Substituted Alkoxysilyldiazenes DOI Creative Commons

Lamine Saadi,

Lydie Valade, Clément Chauvier

et al.

Chemical Science, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Organoalkoxysilanes (e.g. R-SiMe3-n (OR') n , 1 ≤ 3 with R = alkyl or aryl) have found various applications in synthetic chemistry and materials science because the silicon-bound alkoxy groups provide unique opportunities for further derivatization transformations. Among few catalytic strategies that allow direct intermolecular introduction of an alkoxysilyl unit onto organic substrate, alkoxysilylation unactivated C-H bonds has barely been achieved despite its potential atom-economy it conveys. In particular, a transition metal-free silylation protocol towards this class organosilicon compounds yet to be reported. We herein describe first general (hetero)arene C(sp2)-H benzylic C(sp3)-H under ambient, conditions using newly-prepared tert-butyl-substituted alkoxysilyldiazenes (tBu-N[double bond, length as m-dash]N-SiMe3-n R' Et, iPr tBu) silylating reagents tBuOK promoter.

Language: Английский

Citations

0
Fluoride-Catalyzed Arylation of α-(Trifluoromethyl)styrene Derivatives with Silicon-Masked, Functionalized Aryl Pronucleophiles DOI
Aliyaah J. M. Rahman, Y. XU, Martin Oestreich

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(30), P. 5636 - 5640

Published: July 25, 2023

An operationally simple transition-metal-free protocol for the arylation of α-(trifluoromethyl)styrene derivatives with silicon-protected functionalized aryl pronucleophiles is disclosed. Catalytic amounts an anionic Lewis base such as fluoride trigger release nucleophile from N-aryl-N'-silyldiazenes by desilylation along denitrogenation. The thus-generated carbon nucleophiles engage in allylic displacement electrophiles to afford corresponding geminal difluoroalkenes.

Language: Английский

Citations

9
Silylation of Allylic C(sp3)–H Bonds Enabled by the Catalytic Generation of Allylpotassium Complexes DOI
Xueyan Zhang, Louis Fensterbank, Clément Chauvier

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(24), P. 16207 - 16214

Published: Dec. 5, 2023

Allylsilanes have long been recognized as key molecular building blocks in organic synthesis that are routinely employed nucleophilic allylating reagents. Although a great deal of catalytic and stoichiometric synthetic strategies available to prepare such allylsilanes from prefunctionalized substrates, the use stable widely alkenes their direct precursors remains underdeveloped. In particular, nonoxidative silylation protocol operating through activation allylic C(sp3)–H bonds has yet be reported. Herein, we describe general for under ambient, transition metal-free conditions using tert-butyl-substituted silyldiazenes (tBu–N═N–SiR3) silicon source. We demonstrate range 1-alkenes readily afford corresponding with nearly complete linear selectivity. A reactivity model involves experimentally characterized η3-allylpotassium intermediates is also proposed account thermodynamically controlled stereoselectivity reaction.

Language: Английский

Citations

6
Ni-catalyzed undirected and regioselective acceptorless dehydrogenative silylation of primary benzylic C(sp3)–H bonds DOI Creative Commons

Qing Yu,

Takafumi Yatabe, Takehiro Matsuyama

et al.

Catalysis Science & Technology, Journal Year: 2024, Volume and Issue: 14(10), P. 2730 - 2738

Published: Jan. 1, 2024

Here, an undirected acceptorless dehydrogenative silylation of benzylic C(sp 3 )–H bonds was developed using a CeO 2 -supported highly dispersed Ni(0) nanocatalyst.

Language: Английский

Citations

2
Bond-Forming Processes Enabled by Silicon-Masked Aryl- and Alkyl-Substituted Diazenes DOI
Lucie Finck, Martin Oestreich

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(22), P. 15531 - 15539

Published: Nov. 7, 2023

Aryl- and alkyldiimides (R–N═NH with R = aryl or alkyl) are elusive intermediates of valuable synthetic use, as they assumed to be transient species in processes involving both carbon (with concomitant loss N2) nitrogen nucleophiles conservation the N═N moiety). The actual compounds fragile such not bench stable which is why have yet found attention deserve. Conversely, early contributions showed that stability parent diimide significantly increased by replacing hydrogen atom a silyl group, but applicability these silicon-protected aryl- alkyldiazenes has been far less explored, part due absence general procedures for their preparation. This Perspective provides an overview underexplored diazene chemistry witnessed considerable progress recent years highlights potential this motif range synthetically useful (catalytic) transformations. rediscovered silicon-masked diazenes constitute versatile platform possessing enhanced tamed reactivity comparison hydrogen-substituted diimides. Aryl, diazenyl, alkyl anionic key can selectively generated situ under Lewis base transition metal catalysis, giving rise novel approaches viable alternatives already existing methodologies.

Language: Английский

Citations

3
Catalytic Generation of Superbasic Carbanions DOI Open Access
Ozora Sasamoto

Journal of Synthetic Organic Chemistry Japan, Journal Year: 2024, Volume and Issue: 82(8), P. 825 - 826

Published: Aug. 1, 2024

Superbasic carbanions such as phenyl anion and t-butyl have been commonly utilized in organic synthesis, typically prepared using stoichiometric organometallic reagents (e.g., alkyllithium, Grignard reagents). The activation of organosilicon compounds with Lewis base represented by Hosomi-Sakurai allylation is another attractive way to generate reactive relatively mild conditions. While this reaction system has extensively investigated so far, its extension superbasic remains unexplored. This short review describes the recent advancements catalytic methodologies for production from compounds.

Language: Английский

Citations

0