Themed collection HOT articles in Organic Chemistry Frontiers for 2014

Chiral iminopyridine oxazoline (IPO) ligands were designed, synthesized and utilized for the first cobalt-catalyzed highly regio- and enantioselective anti-Markovnikov hydroboration of 1,1-disubstituted aryl alkenes. These novel IPO ligands will likely be of high value for asymmetric transformations with first-row transition metals.

Using a combination of ketones and Selectfluor to mimic α-fluoroketones, formal fluorine-atom-transfer radical addition (F-ATRA) reactions were successfully developed in high efficiency.

A novel synthesis of 1H-indazoles via copper-catalyzed cross-coupling/cyclization of 2-bromoaryl oxime acetates and amines is reported.

A scalable approach to access various pharmaceutical and structurally intriguing N-substituted phthalimides via double aminocarbonylations has been established under atmospheric CO pressure with a robust Pd-NHC complex at a low catalyst loading.

We describe here step-economical, function-oriented strategies towards the syntheses of potent kinase inhibitors inspired by the natural product staurosporine.

A robust catalyst derived from NiCl₂·(DME) and acenaphthoimidazolium chloride exhibited high activity towards the challenging amination of bulky and heterocyclic aryl tosylates with secondary and primary amines under mild reaction conditions.

The first phosphine-catalyzed cyclopropanation reaction via covalent ylide catalysis has been realized with high efficiency in the presence of sidearm-assisted phosphine catalysts.

A p-nitrobenzyloxycarbonyl/bis-Boc strategy was developed for efficient synthesis of versatile PNA–peptide conjugates.

1-Amino-isoquinoline-N-oxides are generated under mild conditions in good yields through a silver(I) and copper(I) catalyzed reaction of 2-alkynylbenzaldoxime with secondary amines.

Monodentate aminocarbene ligands, both NHC and cAAC, are capable of stabilizing low-coordinate iron(I) compounds.

Near-infrared absorbing heterocyclic quinoid molecules have been developed as donor materials for organic photovoltaic devices.

Polycyclic aromatics undergo [4 + 4] photocycloaddition to give tricyclic polyene products.

The I₂-mediated oxidative dimerization of tetrahydropyrroloindoles allows the convenient and efficient synthesis of target molecules.

A sequence of Mukaiyama aldol and radical hydrogen transfer reactions was applied to α-alkoxy and α-aminoaldehydes for the synthesis of propionate motifs and subunits thereof.

A facile approach for the synthesis of benzo[3.1.0]bicycloalkanes via alkylation/cyclopropanation cascade reactions of benzyl bromide with triphenylphosphonium bromide.

The direct difluoromethylation of electron-poor aryl iodides, as well as heteroaryl and β-styryl iodides, using TMSCF₂H at ambient temperature was developed.

A novel type of open-chain chiral chelating olefin bearing a simple monophosphite unit with a binaphthyl backbone was designed and synthesized for asymmetric catalysis.

A high-yielding approach for the diastereoselective syntheses of the four (5′S)- and (5′R)-5′,8-cyclopurine lesions and their phosphoramidites has been developed.

The fluoride ion detection limit is at the micromolar level.

ZnCl₂ effectively facilitates selective monofluorination of methylene compounds by inhibiting the undesired overfluorination.

The reduction (deuteration) of oxygenated arenes can be achieved by Pd/CM-phos catalyst system via a tosylation pathway.

Deconjugated linear 3,5-dienones with substantial substitutions were used in β,ε-regioselective Diels–Alder cycloadditions with 3-olefinic oxindoles via trienamine catalysis of cinchona-based primary amines.

Vanadium(III) oxide catalyzes the direct fluorination of C(sp³)–H groups with Selectfluor.

A bis-carbene-stabilized ethynyl radical cation, a purely organic mixed valence compound, is indefinitely air stable.

Different types of fused heteroaromatic diones have been successfully prepared through the concise intramolecular double Friedel–Crafts acylation strategy.

The combination of Pd(cod)Cl₂ and L9 allows for the selective 1,4-hydroamination of a series of acyclic and cyclic dienes with a variety of aromatic and aliphatic amines under relatively mild conditions. The reaction gives exclusive formation of synthetically useful allylic amines with high regio- and chemoselectivity and does not need any additives.

Efficient sterically demanding aryl–alkyl Suzuki–Miyaura coupling between di-ortho-substituted aryl halides and secondary alkylboronic acids has been achieved with a Pd-AntPhos catalyst.

A high-yielding route to β-methyl-α-methylene-γ-butyrolactone, a monomer for the production of high-performance engineering bioplastics, from biorenewable and inexpensive itaconic acid has been developed.

Three-component reaction of carbodiimides, acyl chlorides, and isocyanides took place smoothly at room temperature to afford 1,4-disubstituted 5-acetamidoimidazoles in good yields.

An Fe-catalyzed highly regio- and diastereoselective reaction of 4-ethynyloxetan-2-ones with different Grignard reagents affording alkynes 3 in good yields with absolute configuration of the β-carbon atom completely inverted has been developed.

The different solvent responses for bipyridinium and trispyridinium-based dynamic imine [2]rotaxanes allow their interconversion with high selectivity.

Sterically disfavored oxazolidines were obtained via a Rh(II)/Ag(I)-catalyzed [3 + 2] exo-cycloaddition reaction. Subsequent hydrolysis gave trans-β-amino-α-hydroxyl ester derivatives in high yields.

A palladium-catalyzed base-accelerated ortho-selective C–H alkenylation of phenols to synthesize bioactive coumarin derivatives was developed featuring a wide substrate scope under mild reaction conditions. Several bioactive molecules were functionalized and several coumarins with bioactive properties were synthesized.

Transition-metal-free radical azidofluorination of unactivated alkenes was successfully achieved in aqueous solution at room temperature with excellent regioselectivity and functional group compatibility.