Search results for "cycloadditions"

1,3-Dipolar cycloadditions in the synthesis of annelated diazines: design of new scaffolds for anticancer and antimicrobial agents

2008

Pauson-Khand reaction of internal dissymmetric trifluoromethyl alkynes. Influence of the alkene on the regioselectivity.

2014

Abstract: The scope of the Pauson-Khand reaction (PKR) of internal trifluoromethyl alkynes, previously described with norbornadiene, is expanded to norbornene and ethylene. A thorough structural analysis of the resulting PK adducts has been carried out to unveil that α-trifluoromethylcyclopentenones are preferred in all cases, independently of the electronic properties of the alkyne. The regioselectivity observed with norbornadiene and ethylene is higher than in the case of norbornene.

Polycyclic aromatic chains on metals and insulating layers by repetitive [3+2] cycloadditions

2020

The vast potential of organic materials for electronic, optoelectronic and spintronic devices entails substantial interest in the fabrication of π-conjugated systems with tailored functionality directly at insulating interfaces. On-surface fabrication of such materials on non-metal surfaces remains to be demonstrated with high yield and selectivity. Here we present the synthesis of polyaromatic chains on metallic substrates, insulating layers, and in the solid state. Scanning probe microscopy shows the formation of azaullazine repeating units on Au(111), Ag(111), and h-BN/Cu(111), stemming from intermolecular homo-coupling via cycloaddition reactions of CN-substituted polycyclic aromatic az…

Unveiling the Different Chemical Reactivity of Diphenyl Nitrilimine and Phenyl Nitrile Oxide in [3+2] Cycloaddition Reactions with (R)-Carvone throug…

2020

The [3+2] cycloaddition (32CA) reactions of diphenyl nitrilimine and phenyl nitrile oxide with (R)-carvone have been studied within the Molecular Electron Density Theory (MEDT). Electron localisation function (ELF) analysis of these three-atom-components (TACs) permits its characterisation as carbenoid and zwitterionic TACs, thus having a different reactivity. The analysis of the conceptual Density Functional Theory (DFT) indices accounts for the very low polar character of these 32CA reactions, while analysis of the DFT energies accounts for the opposite chemoselectivity experimentally observed. Topological analysis of the ELF along the single bond formation makes it possible to characteri…

Tandem Reactions of 1,2,4-Oxadiazoles with Allylamines

2011

A reaction of 3-chloro-1,2,4-oxadiazoles with allylamine and diallylamine has been investigated. 3,3a,4,5-Tetrahydroisoxazolo[3,4-d]pyrimidines are produced through a tandem ANRORC/[3 + 2]cycloaddition pathway consisting of the addition of allylamine to the 1,2,4-oxadiazole, followed by ring opening, nitrone formation, and finally cycloaddition. 3-N-Allylamino-1,2,4-oxadiazoles were also obtained as minor products through a classical SNAr. Conversely, a reaction with diallylamine produces 3-N,N-diallylamino-1,2,4-oxadiazole and imidazoline through tandem SNAr/aziridination and nucleophilic ring opening.

PtII versus PdII-assisted [2+3] cycloadditions of nitriles and nitrone. Synthesis of nitrile-derived arylamido platinum(II) and Δ4-1,2,4-oxadiazoline…

2019

Abstract The reactions of bis(organonitrile) platinum(II) complexes trans-[PtCl2(N CR)2] (R = C6H4(p-HC O), CH2C6H4(p-CH3)) with pyrroline N-oxide −O+N CHCH2CH2CMe2 afford arylamido platinum(II) complexes trans-[PtCl2{(O CR)N CCH2CH2CMe2NH}2] (R = C6H4(p-HC O) (1), CH2C6H4(p-CH3) (2)). The spectral data of 1 and 2 show that the oxadiazoline rings in both cases have opened by a spontaneous N O bond cleavage to form (Z)-p-formyl-N-(5,5-dimethylpyrrolidin-2-ylidene)benzamide or (Z)-N-(5,5-dimethylpyrrolidin-2-ylidene)-2-p-tolylacetamide ligands, respectively, where the N-atoms of the benzamide or acetamide moieties coordinate to platinum(II) metal centre in trans positions. However, the reacti…

Ortho -Functionalized Aryltetrazines by Direct Palladium-Catalyzed C−H Halogenation: Application to Fast Electrophilic Fluorination Reactions

2016

International audience; A general catalyzed direct C-H functionalization of s-tetrazines is reported. Under mild reaction conditions, N-directed ortho-C-H activation of tetrazines allows the introduction of various functional groups, thus forming carbon-heteroatom bonds: C-X (X=I, Br, Cl) and C-O. Based on this methodology, we developed electrophilic mono- and poly-ortho-fluorination of tetrazines. Microwave irradiation was optimized to afford fluorinated s-aryltetrazines, with satisfactory selectivity, within only ten minutes. This work provides an efficient and practical entry for further accessing highly substituted tetrazine derivatives (iodo, bromo, chloro, fluoro, and acetate precurso…