Metal-mediated cleavage of unsaturated C-C bonds

Chan, Antony P. Y.; Sergeev, Alexey G.

doi:10.1016/j.ccr.2020.213213

Cited by 34 publications

(12 citation statements)

References 355 publications

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“…Analogous formation of silepin V by an excited state cyclic alkyl amino silylene was demonstrated by Iwamoto (Scheme a) . Intermolecular dearomatization by silylenes of more reactive azulene or naphthalene was also reported by Iwamoto and Chen et al Besides these examples, only few low-valent main group and transition-metal complexes capable of aromatic C–C bond cleavage were reported.…”

Section: Introductionmentioning

confidence: 99%

Room Temperature Intermolecular Dearomatization of Arenes by an Acyclic Iminosilylene

et al. 2023

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A novel nontransient acyclic iminosilylene (1), bearing a bulky super silyl group (−Si t Bu 3 ) and N-heterocyclic imine ligand with a methylated backbone, was prepared and isolated. The methylated backbone is the feature of 1 that distinguishes it from the previously reported nonisolable iminosilylenes, as it prevents the intramolecular silylene center insertion into an aromatic C−C bond of an aryl substituent. Instead, 1 exhibits an intermolecular Buchner-ring-expansion-type reactivity; the silylene is capable of dearomatization of benzene and its derivatives, giving the corresponding silicon analogs of cycloheptatrienes, i.e. silepins, featuring seven-membered SiC 6 rings with nearly planar geometry. The ring expansion reactions of 1 with benzene and 1,4bis(trifluoromethyl)benzene are reversible. Similar reactions of 1 with N-heteroarenes (pyridine and DMAP) proceed more rapidly and irreversibly forming the corresponding azasilepins, also with nearly planar seven-membered SiNC 5 rings. DFT calculations reveal an ambiphilic nature of 1 that allows the intermolecular aromatic C−C bond insertion to occur. Additional computational studies, which elucidate the inherent reactivity of 1, the role of the substituent effect, and reaction mechanisms behind the ring expansion transformations, are presented.

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Section: Introductionmentioning

confidence: 99%

Room Temperature Intermolecular Dearomatization of Arenes by an Acyclic Iminosilylene

et al. 2023

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“…It is important for the preparation aromatic compounds from lignin as a sustainable alternative to conventional crude oil based methods. [1][2][3] It is also a very fundamental reaction in industrial organic synthesis and in valorisation of biomass i.e. oils, terpenes 4 .…”

Section: Introductionmentioning

confidence: 99%

Oxidative cleavage of C–C double bond in cinnamic acids with hydrogen peroxide catalysed by vanadium(v) oxide

Horvat

Iskra

2022

Green Chem.

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“…As a result, its use is more widespread within the synthetic community for reaction of ketohydroxylation to generate hydroxy ketones and oxidative cleavage reactions to give the corresponding carbonyl compounds. [ 15 ] The mechanism indicates a concerted [3+2]‐cycloaddition between the olefin and RuO 4 ( I ) to lead to ruthenium intermediate ( II ) which is oxidized to ruthenate III (Figure 2). This cyclic ruthenium‐ester plays a key role in all transformations.…”

Section: Ruthenium‐mediated Syn‐dihydroxylationmentioning

confidence: 99%

Recent Advances on Catalytic Osmium‐Free Olefin syn‐Dihydroxylation

Achard

Bellemin‐Laponnaz

2020

Eur J Org Chem

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The syn‐dihydroxylation of olefinic group is one of the most important synthetic transformations which leads to the controlled formation of syn‐diol. Such 1,2‐diol structure is integrated into more complex architectures and substantially participates in the development of biologically active molecules and other fine chemicals. This minireview describes recent evolution of this research field in the past decade, surveying osmium‐free and more eco‐compatible system and in particular the direct oxidation of olefins catalyzed by transition metal complexes.

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Metal-mediated cleavage of unsaturated C-C bonds

Cited by 34 publications

References 355 publications

Room Temperature Intermolecular Dearomatization of Arenes by an Acyclic Iminosilylene

Room Temperature Intermolecular Dearomatization of Arenes by an Acyclic Iminosilylene

Oxidative cleavage of C–C double bond in cinnamic acids with hydrogen peroxide catalysed by vanadium(v) oxide

Recent Advances on Catalytic Osmium‐Free Olefin syn‐Dihydroxylation

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