Unique cascade ring-opening/cyclization reaction of azlactones and DBU or DBN: Synthesis of new pyrrolam A analogues

1-Azabicyclo[3.3.0]oct-3-en-2-one derivatives were synthesized efficiently through the facile cascade reaction of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) or 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) with arylidene azlactones. This research provides a straightforward procedure for the synthesis of a novel class of multicyclic semi-alkaloids which shows good antimicrobial activity. Under catalyst-free, mild, and solventless condition, a wide range of fused tricyclic derivatives was obtained in high yields.     

Reactions of cisplatin hydrolytes, cis-[Pt(15NH3)2(H2O) 2]2+, with N-acetyl-L-cysteine

The reaction of cis-[Pt(¹⁵NH₃)2(H₂O) ₂] ²⁺ (3) with N-acetylcysteine [H₃accys] was investigated in aqueous solution. In this reaction, the ammine in the platinum complex formed was liberated. A mono-dentate sulfur-boundplatinum(II) product cis-[Pt(¹⁵NH₃)₂(H₂O)(H2accys-S)]⁺ (7) and six-membered che-late ring complex cis-[Pt(¹⁵NH₃)₂ (Haccys-S,O)] (8) were formed in solution. The dinuclear sulfur-bridged complex 9, giving a broad peak in ¹⁵N NMR, was also observed, but only present in very tiny amounts. The mass spectrometry (ES-MS) was undertaken from this re action, and the product detected was only the dinuclear sulfur bridged platinum species and species related to it by ammine loss.     

Enantioselective synthesis of bicylco[3.2.1]octan-8-ones using a tandem Michael-Henry reaction

Bicyclo[3.2.1]octan-8-ones have been prepared from a tandem Michael-Henry reaction between cyclohexane-1,2-diones and nitroalkenes using a quinine-derived thiourea as the catalyst. Although four stereogenic centers were created during the reaction, only two diastereomers were obtained in good diastereoselectivity and high enantioselectivity (92-99% ee). When 3-methylcyclohexane-1,2-dione (R¹=Me) was used as the substrate, only the regioisomeric product of the corresponding thermodynamic enolate was obtained.     

Palladium-catalyzed asymmetric allylic alkylation (AAA) with alkyl sulfones as nucleophiles

An efficient palladium-catalyzed AAA reaction with a simple α-sulfonyl carbon anion as nucleophiles is presented for the first time. Allyl fluorides are used as superior precursors for the generation of π-allyl complexes that upon ionization liberate fluoride anions for activation of silylated nucleophiles. With the unique bidentate diamidophosphite ligand ligated palladium as catalyst, the in situ generated α-sulfonyl carbon anion was quickly captured by the allylic intermediates, affording a series of chiral homo-allylic sulfones with high efficiency and selectivity. This work provides a mild in situ desilylation strategy to reveal nucleophilic carbon centers that could be used to overcome the pK_a limitation of “hard” nucleophiles in enantioselective transformations.

A variety of “hard” α-sulfonyl carbanions of aryl, heteroaryl and alkyl sulfones were successfully employed as nucleophiles in palladium-catalyzed asymmetric allylic alkylation with excellent enantioselectivities.     

Strong and Weak Solutions to Second Order Differential Inclusions Governed by Monotone Operators

In this paper we introduce the concept of a weak solution for second order differential inclusions of the form u″(t) ∈ Au(t) + f(t), where A is a maximal monotone operator in a Hilbert space H. We prove existence and uniqueness of weak solutions to two point boundary value problems associated with such kind of equations. Furthermore, existence of (strong and weak) solutions to the equation above which are bounded on the positive half axis is proved under the optimal condition tf(t) ∈ L ¹(0, ∞; H), thus solving a long-standing open problem (for details, see our comments in Section 3 of the paper). Our treatment regarding weak solutions is similar to the corresponding theory related to the first order differential inclusions of the form f(t) ∈ u′(t) + Au(t) which has already been well developed.     

Row–column interaction models,with an R implementation

We propose a family of models called row–column interaction models (RCIMs) for two-way table responses. RCIMs apply some link function to a parameter (such as the cell mean) to equal a row effect plus a column effect plus an optional interaction modelled as a reduced-rank regression. What sets this work apart from others is that our framework incorporates a very wide range of statistical models, e.g., (1) log-link with Poisson counts is Goodman’s RC model, (2) identity-link with a double exponential distribution is median polish, (3) logit-link with Bernoulli responses is a Rasch model, (4) identity-link with normal errors is two-way ANOVA with one observation per cell but allowing semi-complex modelling of interactions of the form  \(\mathbf{A}\mathbf{C}^T\) , (5) exponential-link with normal responses are quasi-variances. Proposed here also is a least significant difference plot augmentation of quasi-variances. Being a special case of RCIMs, quasi-variances are naturally extended from the \(M=1\) linear/additive predictor  \(\eta \) case (within the exponential family) to the \(M>1\) case (vector generalized linear model families). A rank-1 Goodman’s RC model is also shown to estimate the site scores and optimums of an equal-tolerances Poisson unconstrained quadratic ordination. New functions within the VGAM R package are described with examples. Altogether, RCIMs facilitate the analysis of matrix responses of many data types, therefore are potentially useful to many areas of applied statistics.     

Lattice Boltzmann simulation of non-Newtonian flows past confined cylinders

A second-order lattice Boltzmann algorithm is used for Power-Law non-Newtonian flow simulation. The shear dependent behavior of the fluid is implemented through calculating the shear locally from the lattice distribution functions. A step by step verification procedure is taken to ensure the accuracy and the physical correctness of the numerical simulation. The flow past a series of tandem arrangement of two cylinders is computed in a confined domain. The effects of Reynolds number, the Power-Law index, and the distance between two cylinders on both the flow field and the drag coefficients of the cylinders are examined in detail.     

Enhancement of catalytic activity of titanosilicalite-1 - sulfated zirconia combination towards epoxidation of 1-octene with aqueous hydrogen peroxide

Summary Titanosilicalite-1 (TS-1) in combination with sulfated zirconia efficiently catalyzes the epoxidation of 1-octene with aqueous hydrogen peroxide. The presence of both octahedral zirconium and sulfate species in the catalysts enhances the epoxidation rates.     

Nanomolar Determination of Methyldopa in the Presence of Large Amounts of Hydrochlorothiazide Using a Carbon Paste Electrode Modified with Graphene Oxide Nanosheets and 3‐(4′‐Amino‐3′‐hydroxy‐biphenyl‐4‐yl)‐acrylic Acid

A novel electrochemical sensor for sensitive detection of methyldopa at physiological pH was developed by the bulk modification of carbon paste electrode (CPE) with graphene oxide nanosheets and 3‐(4′‐amino‐3′‐hydroxy‐biphenyl‐4‐yl)‐acrylic acid (3,′AA). Applying square wave voltammetry (SWV), in phosphate buffer solution (PBS) of pH 7.0, the oxidation current increased linearly with two concentration intervals of methyldopa, one is 1.0×10^?8–1.0×10^?6 M and the other is 1.0×10^?6–4.5×10^?5 M. The detection limit (3σ) obtained by SWV was 9.0 nM. The modified electrode was successfully applied for simultaneous determination of methyldopa and hydrochlorothiazide. Finally, the proposed method was applied to the determination of methyldopa and hydrochlorothiazide in some real samples.     

An Eco‐friendly Three Component Manifold for the Synthesis of α‐Aminophosphonates under Catalyst and Solvent‐free Conditions,X‐ray Characterization and Their Evaluation as Anticancer Agents

A series of α‐aminophosphonates were synthesized through one‐pot condensation of aryl aldehydes, aryl amines and diethyl phosphite in the absence of any catalyst and organic solvents. All the synthesized α‐aminophosphonates were characterized by spectral and elemental analysis and in the case of compound 4j by X‐ray crystallography. Some of these new α‐aminophosphonate derivatives were found to have cytotoxic activity on the cancer cell line DU145 in vitro by the MTT method.