Several derivatives of a series that share a thienoisoquinoline scaffold have demonstrated potent activity against cancer cell lines A549, HeLa, HCT-116, and MDA-MB-231 in the submicromolar concentration range. Structure-activity relationship (SAR) studies on a range of derivatives aided in identifying key pharmacophores in the lead compound. A series of compounds have been identified as the most promising with submicromolar IC50 values against a lung cancer cell line (A549). Microscopy studies of cancer cells treated with the lead compound revealed that it causes mitotic arrest and disrupts microtubules. Further evaluation via an in vitro microtubule polymerization assay and competition studies indicate that the lead compound binds to tubulin via the colchicine site.

Primary hydroxylamines, RNHOH, decompose readily in the presence of transition metal ions. We show that this reactivity can be arrested by ligand design via an intramolecular hydrogen bond. Six metal complexes with an intact NHOH group were synthesized and crystallographically characterized. The Cu-hydroxylamine complexes can catalyze the aerobic oxidation of benzylic alcohols.

Sulfonylated pyridines were synthesized in moderate to excellent yields, with a wide scope of substituted pyridines and sulfinate salts as starting materials, by an iron-catalyzed SNAr reaction. This new methodology exhibits advantages for the synthesis of these useful substrates, such as the use of a readily available, inexpensive catalyst, prevention of the disproportionation of the sulfinate salts, and, more importantly, providing access to electron-rich pyridine substrates.

The simultaneous synthesis of 5-hydroxymethyl-2-furoic acid and 2,5-hydroxymethylfuran from biomass-derived 5-hydroxymethyl furan was developed using a solvent-free mechanochemical approach.

As carbon-carbon bonds are an essential bond type in Nature, reactions that form C-C bonds are of great interest in organic chemistry. Among the most popular C-C bond formation methods with aromatic systems are palladium-catalyzed coupling reactions, such as the Heck, Suzuki, Negishi and Stille reactions. Even though these methods are efficient, they produce stoichiometric amounts of high molecular weight byproducts, placing them in conflict with the increasingly important ideas of sustainable reactions and green chemistry. In contrast, palladium-catalyzed desulfinative coupling reactions produce minimal waste; in general, only hydrogen halides or alkali halides are formed as byproducts in addition to SO2 gas, which can potentially be recycled. This microreview provides a brief historic overview on palladium-catalyzed coupling reactions with organosulfur compounds, with the main focus on the use of sulfinate salts as nucleophilic or electrophilic reaction partners. Various methods to access the sulfinate salts, and the coupling reactions of sulfonyl precursors that proceed through sulfinic acid/salt intermediates generated in situ are also discussed.

A range of aryl sulfinates can be oxidatively dimerized to generate substituted biphenyls with concomitant extrusion of sulfur dioxide with a palladium catalyst. Catalytic amounts of TEMPO and excess oxygen are utilized as oxidants to regenerate the palladium catalyst.

Two experimental approaches to the synthesis of a scarcely reported biologically active thienoisoquinoline system are demonstrated. A 5-step linear synthesis employing a palladium-catalyzed decarboxylative cross-coupling and functionalization sequence allowed for the preparation of a diverse range of substituted thienoisoquinoline systems. Alternatively the palladium-catalyzed decarboxylative cross-coupling and CH activation steps can be telescoped to produce a one-pot reaction sequence that provides efficient access to aryl-substituted thienoisoquinolines.

An unsymmetric ligand bearing a salicylimine side and a 2-nitrobenzenesufonamide side has been synthesized in two simple steps. Complexations with Cu(II), Fe(III) and Co(II) - which oxidizes to Co(III) once complexed - indicate that the ligand can be either bidentate or tridentate depending on the geometric preferences of the metal ion and whether the sulfonamide is deprotonated. The obtained crystal structures are also stabilized via hydrogen bonds and pi-pi stacking interactions. Crown Copyright (c) 2013 Published by Elsevier B.V. All rights reserved.