In order to quantify the electrophilic reactivities of common Michael acceptors, we measured the kinetics of the reactions of monoacceptor-substituted ethylenes (HC═CH-Acc, 1) and styrenes (PhCH═CH-Acc, 2) with pyridinium ylides 3, sulfonium ylide 4, and sulfonyl-substituted chloromethyl anion 5. Substitution of the 57 measured second-order rate constants (log k) and the previously reported nucleophile-specific parameters N and s for 3-5 into the correlation log k = s(E + N) allowed us to calculate 15 new empirical electrophilicity parameters E for Michael acceptors 1 and 2. The use of the same parameters s, N, and E for these different types of reactions shows that all reactions proceed via a common rate-determining step, the nucleophilic attack of 3-5 at the Michael acceptors with formation of acyclic intermediates, which subsequently cyclize to give tetrahydroindolizines (stepwise 1,3-dipolar cycloadditions with 3) and cyclopropanes (with 4 and 5), respectively. The electrophilicity parameters E thus determined can be used to calculate the rates of the reactions of Michael acceptors 1 and 2 with any nucleophile of known N and s. DFT calculations were performed to confirm the suggested reaction mechanisms and to elucidate the origin of the electrophilic reactivities. While electrophilicities E correlate poorly with the LUMO energies and with Parr's electrophilicity index ω, good correlations were found between the experimentally observed electrophilic reactivities of 44 Michael acceptors and their calculated methyl anion affinities, particularly when solvation by dimethyl sulfoxide was taken into account by applying the SMD continuum solvation model. Because of the large structural variety of Michael acceptors considered for these correlations, which cover a reactivity range of 17 orders of magnitude, we consider the calculation of methyl anion affinities to be the method of choice for a rapid estimate of electrophilic reactivities.
Herein we report the first example of chiral recognition and kinetic resolution of aromatic amine guests using supramolecular nanocapsules assembled from cyclodextrin derivatives in nonpolar media. With these nanocapsules, an extremely high chiral recognition of 1-(1-naphthyl)ethylamine (1) in cyclohexane was achieved, with a binding selectivity of up to 41 for (S)-1 over (R)-1. In addition, kinetic resolution of 1 through enantioselective N-acylation was accomplished with an enantiomeric excess of up to 91%.
Nickel complexes of a series of β-diketiminate ligands ((R)L(-), deprotonated form of 2-substituted N-[3-(phenylamino)allylidene]aniline derivatives (R)LH, R = Me, H, Br, CN, and NO2) have been synthesized and structurally characterized. One-electron oxidation of the neutral complexes [Ni(II)((R)L(-))2] by AgSbF6 or [Ru(III)(bpy)3](PF6)3 (bpy = 2,2'-bipyridine) gave the corresponding metastable cationic complexes, which exhibit an EPR spectrum due to a doublet species (S = 1/2) and a characteristic absorption band in near IR region ascribable to a ligand-to-ligand intervalence charge-transfer (LLIVCT) transition. DFT calculations have indicated that the divalent oxidation state of nickel ion (Ni(II)) is retained, whereas one of the β-diketiminate ligands is oxidized to give formally a mixed-valence complex, [Ni(II)((R)L(-))((R)L(•))](+). Thus, the doublet spin state of the oxidized cationic complex can be explained by taking account of the antiferromagnetic interaction between the high-spin nickel(II) ion (S = 1) and the organic radical (S = 1/2) of supporting ligand. A single-crystal structure of one of the cationic complexes (R = H) has been successfully determined to show that both ligands in the cationic complex are structurally equivalent. On the basis of theoretical analysis of the LLIVCT band and DFT calculations as well as the crystal structure, the mixed-valence complexes have been assigned to Robin-Day class III species, where the radical spin is equally delocalized between the two ligands to give the cationic complex, which is best described as [Ni(II)((R)L(0.5•-))2](+). One-electron reduction of the neutral complexes with decamethylcobaltocene gave the anionic complexes when the ligand has the electron-withdrawing substituent (R = CN, NO2, Br). The generated anionic complexes exhibited EPR spectra due to a doublet species (S = 1/2) but showed no LLIVCT band in the near-IR region. Thus, the reduced complexes are best described as the d(9) nickel(I) complexes supported by two anionic β-diketiminate ligands, [Ni(I)((R)L(-))2](-). This conclusion was also supported by DFT calculations. Substituent effects on the electronic structures of the three oxidation states (neutral, cationic, and anionic) of the complexes are systematically evaluated on the basis of DFT calculations.
Kinetics of the reactions of bissulfonyl ethylenes with various carbanions, a sulfur ylide, and siloxyalkenes have been investigated photometrically at 20 °C. The second-order rate constants have been combined with the known nucleophile- specific parameters N and s(N) for the nucleophiles to calculate the empirical electrophilicity parameters E of bissulfonyl ethylenes according to the linear free energy relationship log k(20 °C)=s(N)(N+E). Structure-reactivity relationships are discussed, and it is shown that the electrophilicity parameters E derived in this work can be employed to define the synthetic potential of bissulfonyl ethylenes as Michael acceptors.
Metal–plastics
adhesion has received much attention from
researchers due to its potential use in various industrial applications.
However, the adhesion of plastics with metals is poor due to the low
surface energy of plastics. Accordingly, the adhesion of plastics
usually requires surface modification or the use of an adhesive primer.
Recently, we developed a polymer surface modification method using
the light-activated chlorine dioxide (ClO2
•) radical as oxidant. In this study, we investigated the adhesion
behavior of PP film modified by this method. Improvements in hydrophilicity
and adhesion property of PP were observed after oxidation. The oxidized
PP film exhibited good adhesive properties with Al plate without any
adhesives, and the adhesion strength could be further enhanced by
increasing the oxidation temperature. Moreover, this study successfully
developed an approach for the electroless metal plating on polymer
surfaces. In addition, we also found that light irradiation only activated
ClO2
• but had no direct modification
on plastics.
The chlorine dioxide radical (ClO2˙) was found to act as an efficient oxidizing agent for the aerobic C–H oxygenation of the side-chain methyl groups in polypropylene under photoirradiation.
A new method for synthesizing polyalkylated/arylated nicotinates is established using a condensation of enamino esters with enones in the presence of FeCl. This method facilitates the introduction of alkyl or aryl groups at any position on demand, which has not been achieved by other procedures.
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