276 research outputs found
[C^N]âAlkenyl Gold(III) Complexes by Proximal RingâOpening of (2âPyridyl)alkylidenecyclopropanes: Mechanistic Insights
This is the peer reviewed version of the following article: J. A. GonzĂĄlez, F. Verdugo, J. L. Mascareñas, F. LĂłpez, C. Nevado, Angew. Chem. Int. Ed. 2020, 59, 20049, which has been published in final form at https://doi.org/10.1002/anie.202007371. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions.Pyridineâsubstituted alkylidenecyclopropanes (PyâACPs) react with gold(III) salts under mild reaction conditions through an unprecedented, proximal ringâopening pathway, to generate highly appealing, catalytically active pyridine alkenyl [C^N]âgold(III) species. Mechanistic studies reveal that the activation of the CâC bond of the ACP takes place through an unusual concerted, Ïâbond metathesis typeâprocessWe thank the European Research Council (ERC Starting grant agreement no. 307948, and Advanced Grant 340055), the Swiss National Science Foundation (SNF 200020_146853), the Legerlotz Stiftung the MINECO (SAF2016â76689âR, CTQ2017â84767âP), the Xunta de Galicia (2015âCP082, ED431C 2017/19, and Centro singular de investigaciĂłn de Galicia accreditation 2019â2022, ED431G 2019/03) and the European Union (European Regional Development FundâERDF) for financial support and the STSM Grant to F. Verdugo from COST Action CA15106S
Scope and Mechanistic Study of the Coupling Reaction of α,ÎČ-Unsaturated Carbonyl Compounds with Alkenes: Uncovering Electronic Effects on Alkene Insertion vs Oxidative Coupling Pathways
The cationic ruthenium-hydride complex [(C6H6)(PCy3)(CO)RuH]+BF4â (1) was found to be a highly effective catalyst for the intermolecular conjugate addition of simple alkenes to α,ÎČ-unsaturated carbonyl compounds to give (Z)-selective tetrasubstituted olefin products. The analogous coupling reaction of cinnamides with electron-deficient olefins led to the oxidative coupling of two olefinic CâH bonds in forming (E)-selective diene products. The intramolecular version of the coupling reaction efficiently produced indene and bicyclic fulvene derivatives. The empirical rate law for the coupling reaction of ethyl cinnamate with propene was determined as follows: rate = k[1]1[propene]0[cinnamate]â1. A negligible deuterium kinetic isotope effect (kH/kD = 1.1 ± 0.1) was measured from both (E)-C6H5CHâC(CH3)CONHCH3 and (E)-C6H5CDâC(CH3)CONHCH3 with styrene. In contrast, a significant normal isotope effect (kH/kD = 1.7 ± 0.1) was observed from the reaction of (E)-C6H5CHâC(CH3)CONHCH3 with styrene and styrene-d8. A pronounced carbon isotope effect was measured from the coupling reaction of (E)-C6H5CHâCHCO2Et with propene (13C(recovered)/13C(virgin) at CÎČ = 1.019(6)), while a negligible carbon isotope effect (13C(recovered)/13C(virgin) at CÎČ = 0.999(4)) was obtained from the reaction of (E)-C6H5CHâC(CH3)CONHCH3 with styrene. Hammett plots from the correlation of para-substituted p-X-C6H4CHâCHCO2Et (X = OCH3, CH3, H, F, Cl, CO2Me, CF3) with propene and from the treatment of (E)-C6H5CHâCHCO2Et with a series of para-substituted styrenes p-Y-C6H4CHâCH2 (Y = OCH3, CH3, H, F, Cl, CF3) gave the positive slopes for both cases (Ï = +1.1 ± 0.1 and +1.5 ± 0.1, respectively). Eyring analysis of the coupling reaction led to the thermodynamic parameters, ÎH⧧ = 20 ± 2 kcal molâ1 and ÎS⧧ = â42 ± 5 eu. Two separate mechanistic pathways for the coupling reaction have been proposed on the basis of these kinetic and spectroscopic studies
An Experimental Biomimetic Platform for Artificial Olfaction
Artificial olfactory systems have been studied for the last two decades mainly from the point of view of the features of olfactory neuron receptor fields. Other fundamental olfaction properties have only been episodically considered in artificial systems. As a result, current artificial olfactory systems are mostly intended as instruments and are of poor benefit for biologists who may need tools to model and test olfactory models. Herewith, we show how a simple experimental approach can be used to account for several phenomena observed in olfaction
The mechanisms of boronate ester formation and fluorescent turn-on in ortho-aminomethylphenylboronic acids
ortho-Aminomethylphenylboronic acids are used in receptors for carbohydrates and various other compounds containing vicinal diols. The presence of the o-aminomethyl group enhances the affinity towards diols at neutral pH, and the manner in which this group plays this role has been a topic of debate. Further, the aminomethyl group is believed to be involved in the turn-on of the emission properties of appended fluorophores upon diol binding. In this treatise, a uniform picture emerges for the role of this group: it primarily acts as an electron-withdrawing group that lowers the pK(a) of the neighbouring boronic acid thereby facilitating diol binding at neutral pH. The amine appears to play no role in the modulation of the fluorescence of appended fluorophores in the protic-solvent-inserted form of the boronic acid/boronate ester. Instead, fluorescence turn-on can be consistently tied to vibrational-coupled excited-state relaxation (a loose-bolt effect). Overall, this Review unifies and discusses the existing data as of 2019 whilst also highlighting why o-aminomethyl groups are so widely used, and the role they play in carbohydrate sensing using phenylboronic acids
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