Synthesis of unsymmetrical biaryl ureas from N-carbamoylimidazoles: kinetics and application

N-Carbamoylimidazoles dissociate in solution to yield imidazole and an isocyanate that may be reacted with another aryl amine to form an unsymmetrical biaryl urea. This paper investigates the reaction kinetics and the influence of electron withdrawing/donating substituents on the reaction of N-carbamoylimidazoles with aniline. The overall reaction mechanism involves two zwitterionic intermediates, formed during dissociation and upon reaction of the liberated isocyanate with aniline. The rate limiting step for the reaction is a base catalysed proton transfer from the second zwitterionic intermediate. Although electron withdrawing substituents on the aryl group hinder dissociation, they significantly increase reaction rates compared to compounds bearing electron donating substituents. The imidazole liberated upon dissociation catalyses the rate determining step so that reactions of dissociated N-carbamoylimidazoles proceed more rapidly than those involving only isocyanates. In addition, the imidazole eliminates the need for anhydrous reaction conditions. The N-carbamoylimidazole methodology was demonstrated by preparing sorafenib, a biaryl urea kinase inhibitor, in good yield and excellent purity.     

A penalized criterion for variable selection in classification

In this paper, the problem of variable selection in classification is considered. On the basis of recent developments in model selection theory, we provide a criterion based on penalized empirical risk, where the penalization explicitly takes into account the number of variables of the considered models. Moreover, we give an oracle-type inequality that non-asymptotically guarantees the performance of the resulting classification rule. We discuss the optimality of the proposed criterion and present an application of the main result to backward and forward selection procedures.     

High-Fidelity,Narcissistic Self-Sorting in the Synthesis of Organometallic Assemblies from Poly-NHC Ligands

Highly selective, narcissistic self-sorting has been observed in the one-pot synthesis of three organometallic molecular cylinders of type [M₃{L-(NHC)₃}₂](PF₆)₃ (M=Ag⁺, Au⁺; L=1,3,5-benzene, triphenylamine, or 1,3,5-triphenylbenzene) from L-(NHC)₃ and silver(I) or gold(I) ions. The molecular cylinders contain only one type of tris-NHC ligand with no crossover products detectable. Transmetalation of the tris-NHC ligands from Ag⁺ to Au⁺ in a one-pot reaction with retention of the supramolecular structures is also demonstrated. High-fidelity self-sorting was also observed in the one-pot reaction of benzene-bridged tris-NHC and tetrakis-NHC ligands with Ag₂O. This study for the first time extends narcissistic self-sorting in metal–ligand interactions from Werner-type complexes to organometallic derivatives.     

Inflation of Finite Lattices Along All-or-nothing Sets

We introduce a new generalization of Alan Day’s doubling construction. For ordered sets \(\mathcal {L}\) and \(\mathcal {K}\) and a subset \(E \subseteq \ \leq _{\mathcal {L}}\) we define the ordered set \(\mathcal {L} \star _{E} \mathcal {K}\) arising from inflation of \(\mathcal {L}\) along E by \(\mathcal {K}\). Under the restriction that \(\mathcal {L}\) and \(\mathcal {K}\) are finite lattices, we find those subsets \(E \subseteq \ \leq _{\mathcal {L}}\) such that the ordered set \(\mathcal {L} \star _{E} \mathcal {K}\) is a lattice. Finite lattices that can be constructed in this way are classified in terms of their congruence lattices.A finite lattice is binary cut-through codable if and only if there exists a 0?1 spanning chain \(\left \{\theta _{i}\colon 0 \leq i \leq n \right \}\) in \(Con(\mathcal {L})\) such that the cardinality of the largest block of ?? _i /?? _i?1 is 2 for every i with 1≤i≤n. These are exactly the lattices that can be constructed by inflation from the 1-element lattice using only the 2-element lattice. We investigate the structure of binary cut-through codable lattices and describe an infinite class of lattices that generate binary cut-through codable varieties.     

Charging megadalton poly(ethylene oxide)s by electrospray ionization. A charge detection mass spectrometry study

Ions from compounds of megadalton (MDa) molecular weight were produced in an electrospray ionization source from solutions of poly(ethylene oxide) (PEO) samples with average molecular weights ranging from 1,000,000 to 7,000,000 Da. Charge detection mass spectrometry (CDMS) has been used to determine the mass of the MDa PEOs. Simultaneous measurement of the charge and velocity of individual ions allows the mass determination of the ion, after calibration of the instrument with independent samples. In addition to the mass spectra, CDMS generates charge-versus-mass plots, which allow investigation of the charging of electrosprayed ions over a broad range of masses. The experimental charging capacity of MDa PEOs is compared with a simple model based on the affinity of alkali cations for oxygen sites and on the electrostatic potential energy of the charged polymer. The charging capacity of PEOs was also investigated as a function of the concentration of and the type of alkali ions.     

Tropylium ion mediated α-cyanation of amines

Tropylium ion mediated α-cyanation of amines is described. Even in the presence of KCN, tropylium ion is capable of oxidizing various amine substrates, and the resulting iminium ions undergo salt metathesis with cyanide ion to produce aminonitriles. The byproducts of this transformation are simply cycloheptatriene, a volatile hydrocarbon, and water-soluble potassium tetrafluoroborate. Thirteen total substrates are shown for the α-cyanation procedure, including a gram scale synthesis of 17β-cyanosparteine. In addition, a tropylium ion mediated oxidative aza-Cope rearrangement is demonstrated.