Showing papers on "Intramolecular reaction published in 2015"
TL;DR: The first synthesis of planar-chiral benzosiloloferrocenes was achieved by the intramolecular reaction of 2-(dimethylhydrosilyl)arylferrocenes by the enantioselective cross dehydrogenative coupling of an sp(2) C-H bond of ferrocene with a Si-H Bond.
89 citations
TL;DR: Experimental evidence indicates that plasmon-induced hot electrons provide the required activation energy for surface plasmons to initiate intermolecular reactions of adsorbed p-nitrothiophenol.
82 citations
TL;DR: In this article, the homopolymerization of acrylate based multivinyl monomers can be kinetically controlled via Cu0-mediated controlled/living radical polymerization in the presence of additional CuII, which enables the efficient promotion of intramolecular cyclization and suppression of intermolecular cross-linking.
Abstract: Polymerization of multifunctional monomers could produce polymers with different functionalities and novel macromolecular architectures However, the ability to control the homopolymerization of multivinyl monomers (MVMs) has always been a challenge Here we demonstrate that the homopolymerization of acrylate based MVMs can be kinetically controlled via Cu0-mediated controlled/living radical polymerization in the presence of additional CuII, which enables the efficient promotion of intramolecular cyclization and suppression of intermolecular cross-linking The gelation is effectively delayed over ca 40% monomer conversion in the concentrated polymerization system ([M] = 409 wt %), which is far higher than the Flory–Stockmayer theory predicts Moreover, closer inspection of the synthesized polymers reveals that single-chain cyclized/knotted polymeric nanoparticles (SCKNPs) are formed due to the nature of one-pot in situ intramolecular reaction and self-cyclization of the propagating polymer chains This
36 citations
TL;DR: In this paper, the intra- vs intermolecular transfer-fluoromethylation of aryl fluoromethymylthio compounds is proposed and shown to have intramolecular reaction.
Abstract: The intra- vs intermolecular transfer-fluoromethylation of aryl fluoromethylthio compounds is proposed. Finely designed ArSCF3 (1a) nicely releases its trifluoromethyl (CF3) group intermolecularly under rhodium catalysis, whereas a difluoromethylated analogue, ArSCF2H compound 1b shows intramolecular reaction.
23 citations
TL;DR: Both the rearrangement and the methods used for structural determination of the products are valuable tools for the preparation of characterization of new small molecule compounds.
Abstract: Invited for this month's cover picture is the group of Professor Mark Peczuh at the University of Connecticut. The cover picture compares the rearrangement of a small molecule to the process of turning a stuffed animal inside out. The recycled, inside-out stuffed animals are both artistic and philosophically provocative. They capture the essence of the rearrangement reaction because the compounds themselves turn inside out over the course of the reaction, extending the diversity of products that can arise from simple starting materials. Small molecules often have functional groups with latent reactivity; under the appropriate conditions, those groups can react with other compounds (e.g., reagents) and also with other groups in the same molecule in an intramolecular reaction. The research team found that the epoxidation of some highly functionalized spiroketal compounds promoted rearrangements of their structures that turned them inside out. Some of the features of the products led them to use X-ray crystallography or a combination of computer-assisted structure elucidation, computation, and a new version of the 1,1-ADEQUATE NMR experiment to determine their structures. For more details, see the Communication on p. 577 ff.
22 citations
TL;DR: In this article, the authors examined how and the possible effect microwaves may have on intramolecular reactions such as those of the Claisen-type rearrangement carried out in dimethyl sulfoxide (DMSO) solvent and in solvent-free, microwave irradiation conditions.
Abstract: This article examined how and the possible effect microwaves may have on intramolecular reactions such as those of the Claisen-type rearrangement carried out in dimethyl sulfoxide (DMSO) solvent and in solvent-free, microwave irradiation conditions. For comparison, the reaction was also performed by conventional heating using an oil bath. 2-Allylphenol was synthesized from allylphenyl ether in DMSO solvent under stirring conditions as a model intramolecular reaction taking place via the Claisen rearrangement using a commercial microwave chemical apparatus together with conventional heating; no enhancement of the reaction occurred. To further examine the influence of microwave irradiation on Claisen rearrangement reactions, we also investigated the transformation of 1-allyloxy-4-methoxybenzene to 2-allyl-4-methoxyphenol under both solvent-free conditions (no stirring) and in DMSO medium; here also no reaction enhancement was observed. This notwithstanding, microwaves did impact the formation of a by-product formed in the latter reaction, which was identified by GC and GC/MS as 4-methoxyphenol, the yield of which was nearly fourfold greater (ca. 6%) under microwave irradiation than under oil-bath heating (ca. 1.5%). The latter suggests that under solvent-free conditions a microwave non-thermal effect influenced the formation of this by-product during the Claisen rearrangement process, contrary to the case where the reaction was performed in DMSO medium for which the yields were identical (ca. 2.5%), regardless of whether the reactant was microwave or oil-bath heated.
12 citations
TL;DR: In this article, the use of bifunctional thiourea catalysts in the intramolecular reaction of a nitronate with conjugated ketones to generate the corresponding γ-nitroketones was described.
Abstract: This paper describes the use of bifunctional thiourea catalysts in the intramolecular reaction of a nitronate with conjugated ketones to generate the corresponding γ-nitroketones. In contrast to our previous studies in this area, we obtained the cis-functionalized systems as the major diastereoisomers in good yields and reasonable selectivities.
7 citations
TL;DR: In this article, a symmetrical bis-nickelporphyrin was prepared in very good yield by oxidative coupling of a nickel(II) enaminoporphyrin.
6 citations
TL;DR: An intermediate of the anellation reaction of phenols and 1,3-dienes could be detected, isolated and characterized as the hydroarylation product as mentioned in this paper, which is the major product of the cis-diastereomer ( cis - 3 / trans - 3 ǫ = 12:1).
5 citations
TL;DR: A new intramolecular reaction involving neighboring tert-butyl-NNO-azoxy and N-nitroamine groups was found, which gave the first representatives of 5-diazo-1,2,3-triazol-4-ones as mentioned in this paper.
Abstract: A new intramolecular reaction involving neighboring (tert-butyl-NNO-azoxy) and N-nitroamine groups was found, which gave the first representatives of 5-diazo-1,2,3-triazol-4-ones: 3-acetoxy- and 3-hydroxy-5-diazo-3,5-dihydro-4H-1,2,3-triazol-4-ones. The structure of the products was confirmed by X-ray diffraction and NMR spectroscopy data.
3 citations
TL;DR: The first planar-chiral benzosiloloferrocenes were synthesized in this article by the intramolecular reaction of 2-(dimethylhydrosilyl)arylferrocenes.
Abstract: The first synthesis of planar-chiral benzosiloloferrocenes was achieved by the intramolecular reaction of 2-(dimethylhydrosilyl)arylferrocenes. The enantioselective cross dehydrogenative coupling of an sp2 C–H bond of ferrocene with a Si–H bond proceeded efficiently with the use of a Rh-chiral diene catalyst.
TL;DR: A versatile synthetic route to new 4-quinolone-based polycyclic systems is described in this paper, where TFA-catalyzed intramolecular reaction of N-unsubstituted quinolone 2-carboxylic acid amides gives structurally diverse compounds, depending on the length of the chain.
Abstract: A versatile synthetic route to new 4-quinolone-based polycyclic systems is described. TFA-catalyzed intramolecular reaction of N-unsubstituted quinolone-2-carboxylic acid amides gives structurally diverse compounds, depending on the length of the chain. Acid treatment of β-oxoamides furnishes 3H-pyrazino[1,2-a]quinoline-4,6-diones, due to the nucleophilic attack of N-1 to the carbonyl group, whereas TFA treatment of δ- and e-oxoamides leads to the formation of tetracyclic compounds by a tandem heteroannulation reaction.
TL;DR: A high-yielding, diastereoselective intramolecular reaction cascade reaction is developed creating three new bonds in a single step, thus providing 2,3,5-substituted furans bearing a ring fused cyclopropyl substituent.
Abstract: A high-yielding, diastereoselective intramolecular reaction cascade reaction is developed creating three new bonds in a single step, thus providing 2,3,5-substituted furans bearing a ring fused cyclopropyl substituent.
TL;DR: Although the transformation succeeds efficiently for indole system, the reaction fails for pyrroles as discussed by the authors, which indicates that the transformation is not suitable for the pyrrole system.
Abstract: Although the transformation succeeds efficiently for indole system the reaction fails for pyrroles.