Water extract of red mud: an efficient and renewable medium for environmentally benign synthesis of 2-amino-4H-chromenes

Molecular Diversity - In this study, an efficient and convenient domino Michael addition/intramolecular cyclization protocol is presented for the synthesis of biologically relevant...     

Nickel(II)-azido/thiocyanato complexes of 1-alkyl-2-(naphthylazo)imidazole

[Ni(NaiR)₂(X)₂] (X = N₃ (3, 4) and NCS (5, 6) complexes are synthesized from the reaction of Ni(ClO₄)₂ · 6H₂O with 1-alkyl-2-(naphthyl-α/β-azo)imidazole (α/β-NaiR) and sodium azide (NaN₃) or ammonium thiocyanate (NH₄NCS) (1:2:2 molar ratio) in methanol solution. The complexes are characterized by elemental, spectroscopic and magnetic study. The distorted octahedral structure has been confirmed by single crystal X-ray diffraction study of [Ni(β-NaiEt)₂(NCS)₂] (6b). Cyclic voltammogram exhibits quasireversible oxidation response at 0.3–0.4 V which is corresponding to Ni(III)/Ni(II) couple along with ligand reductions at negative potential to SCE reference electrode.     

The skeletal rearrangement of gold- and platinum-catalyzed cycloisomerization of cis-4,6-dien-1-yn-3-ols: pinacol rearrangement and formation of bicyclo[4.1.0]heptenone and reorganized styrene derivatives

With gold and platinum catalysts, cis-4,6-dien-1-yn-3-ols undergo cycloisomerizations that enable structural reorganization of cyclized products chemoselectively. The AuCl3-catalyzed cyclizations of 6-substituted cis-4,6-dien-1-yn-3-ols proceeded via a 6-exo-dig pathway to give allyl cations, which subsequently undergo a pinacol rearrangement to produce reorganized cyclopentenyl aldehyde products. Using chiral alcohol substrates, such cyclizations proceed with reasonable chirality transfer. In the PtCl2-catalyzed cyclization of 7,7-disubstituted cis-4,6-dien-1-yn-3-ols, we obtained exclusively either bicyclo[4.1.0]heptenones or reorganized styrene products with varied substrate structures. On the basis of the chemoselectivity/structure relationship, we propose that bicyclo[4.1.0]heptenone products result from 6-endo-dig cyclization, whereas reorganized styrene products are derived from the 5-exo-dig pathway. This proposed mechanism is supported by theoretic calculations.     

Mild and practical stereoselective synthesis of (Z)- and (E)-allyl bromides from Baylis-Hillman adducts using Appel agents (PPh3/CBr4): a facile synthesis of semiplenamides C and E

Appel agents (PPh₃/CBr₄) have been utilized for high-yielding stereoselective synthesis of (Z)- and (E)-allyl bromides from Baylis-Hillman adducts at room temperature. The method has been applied for the synthesis of naturally occurring bioactive fatty acid amides, semiplenamides C and E.     

Helical Hairpin Structure of a Potent Antimicrobial Peptide MSI‐594 in Lipopolysaccharide Micelles by NMR Spectroscopy

Essential understanding : Elucidation of structural requirements and interactions of antimicrobial peptides with lipopolysaccharide (LPS) are essential to understand the mechanism of action of antimicrobial peptides. The highly active antimicrobial peptide MSI‐594 (see figure for electrostatic potential surface) acquires a novel helical hairpin structure in complex with LPS. The structure and interactions of MSI‐594 with LPS presented here provide important insights into the mechanism of outer membrane permeabilization by antimicrobial peptides.

     

Gold-catalyzed synthesis of 1,3-disubstituted benzenes through tandem allylation/cyclization reaction of alkynals

Treatment of alkynals with 2-substituted allylsilanes and PPh₃AuCl/AgOTf (5/3 mol%) catalyst led to formation of 1,3-disubstituted benzenes efficiently. This reaction sequence comprises an initial allylation of aldehyde, followed by cycloisomerization of enynes; PPh₃AuOTf is active in both steps.     

Inventory models for defective items incorporating marketing decisions with variable production cost

This paper investigates the finite replenishment inventory models of a single product with imperfect production process. In this process, a certain fraction or a random number of produced items are defective. These non-conforming items are rejected or reworked or if they reached to the customer, refunded. Here, a generalised unit cost function is formulated incorporating the several factors like raw material, labour, replenishment rate and others factors of the manufacturing system. The rate of replenishment is considered to be a variable. The selling price of an unit is determined by a mark-up over the production cost. Optimum production of the product is suggested to have maximum profit using a gradient based mathematical programming technique for optimization. Finally, numerical examples are given to illustrate the results and the significant features of the production system. As a particular case, the result of the perfect system (without defective items) are obtained. Also, the effect of changes in the selling rate, defectiveness, production cost and other parameters on the optimal average profit are graphically presented. Some interesting decisions regarding production policy are established.     

Intramolecular Direct Dehydrohalide Coupling Promoted by KO(t)Bu: Total Synthesis of Amaryllidaceae Alkaloids Anhydrolycorinone and Oxoassoanine

A transition-metal-free intramolecular dehydrohalide coupling via intramolecular homolytic aromatic substitution (HAS) with aryl radicals has been developed in the presence of potassium tert-butoxide and an organic molecule as the catalyst. The methodology has been applied to a concise synthesis of Amaryllidaceae alkaloids viz. oxoassoanine (1b), anhydrolycorinone (1d), and other related structures. Interestingly, the method also works only in the presence of potassium tert-butoxide.