Themed collection HOT articles in Organic Chemistry Frontiers for 2014
Asymmetric cobalt catalysts for hydroboration of 1,1-disubstituted alkenes
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.
Formal fluorine atom transfer radical addition: silver-catalyzed carbofluorination of unactivated alkenes with ketones in aqueous solution
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.
Efficient access to 1H-indazoles via copper-catalyzed cross-coupling/cyclization of 2-bromoaryl oxime acetates and amines
A novel synthesis of 1H-indazoles via copper-catalyzed cross-coupling/cyclization of 2-bromoaryl oxime acetates and amines is reported.
Efficient and scalable Pd-catalyzed double aminocarbonylations under atmospheric pressure at low catalyst loadings
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.
Function through bio-inspired, synthesis-informed design: step-economical syntheses of designed kinase inhibitors
We describe here step-economical, function-oriented strategies towards the syntheses of potent kinase inhibitors inspired by the natural product staurosporine.
Acenaphthoimidazolium chloride-enabled nickel-catalyzed amination of bulky aryl tosylates
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.
A sidearm-assisted phosphine for catalytic ylide intramolecular cyclopropanation
The first phosphine-catalyzed cyclopropanation reaction via covalent ylide catalysis has been realized with high efficiency in the presence of sidearm-assisted phosphine catalysts.
Facile solid-phase synthesis of PNA–peptide conjugates using pNZ-protected PNA monomers
A p-nitrobenzyloxycarbonyl/bis-Boc strategy was developed for efficient synthesis of versatile PNA–peptide conjugates.
Generation of 1-amino-isoquinoline-N-oxides via a tandem reaction of 2-alkynylbenzaldoxime with secondary amines in the presence of silver(I) and copper(I)
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.
Two- and three-coordinate formal iron(I) compounds featuring monodentate aminocarbene ligands
Monodentate aminocarbene ligands, both NHC and cAAC, are capable of stabilizing low-coordinate iron(I) compounds.
Near-infrared absorbing heterocyclic quinoid donors for organic solar cell devices
Near-infrared absorbing heterocyclic quinoid molecules have been developed as donor materials for organic photovoltaic devices.
Enyne [4 + 4] photocycloaddition with polycyclic aromatics
Polycyclic aromatics undergo [4 + 4] photocycloaddition to give tricyclic polyene products.
Highly efficient and stereocontrolled oxidative coupling of tetrahydropyrroloindoles: synthesis of chimonanthines, (+)-WIN 64821 and (+)-WIN 64745
The I2-mediated oxidative dimerization of tetrahydropyrroloindoles allows the convenient and efficient synthesis of target molecules.
Stereocontrolled synthesis of propionate motifs from L-lactic and L-alanine aldehydes. A DFT study of the hydrogen transfer under endocyclic control
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.
Stereospecific synthesis of highly functionalized benzo[3.1.0]bicycloalkanes via multistep cascade reactions
A facile approach for the synthesis of benzo[3.1.0]bicycloalkanes via alkylation/cyclopropanation cascade reactions of benzyl bromide with triphenylphosphonium bromide.
Copper-mediated difluoromethylation of electron-poor aryl iodides at room temperature
The direct difluoromethylation of electron-poor aryl iodides, as well as heteroaryl and β-styryl iodides, using TMSCF2H at ambient temperature was developed.
Design of a new series of chiral phosphite–olefin ligands and their application in asymmetric catalysis
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 problem solving approach for the diastereoselective synthesis of (5′S)- and (5′R)-5′,8-cyclopurine lesions
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.
A green fullerene derivative as a fluoride ion sensor
The fluoride ion detection limit is at the micromolar level.
Selective monofluorination of active methylene compounds: the important role of ZnCl2 in inhibiting overfluorination
ZnCl2 effectively facilitates selective monofluorination of methylene compounds by inhibiting the undesired overfluorination.
Palladium-catalyzed reductive cleavage of tosylated arenes using isopropanol as the mild reducing agent
The reduction (deuteration) of oxygenated arenes can be achieved by Pd/CM-phos catalyst system via a tosylation pathway.
Trienamine catalysis with linear deconjugated 3,5-dienones
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-catalyzed C(sp3)–H fluorination reactions
Vanadium(III) oxide catalyzes the direct fluorination of C(sp3)–H groups with Selectfluor.
Singlet carbenes as mimics for transition metals: synthesis of an air stable organic mixed valence compound [M2(C2)+˙; M = cyclic(alkyl)(amino)carbene]
A bis-carbene-stabilized ethynyl radical cation, a purely organic mixed valence compound, is indefinitely air stable.
A concise method to prepare novel fused heteroaromatic diones through double Friedel–Crafts acylation
Different types of fused heteroaromatic diones have been successfully prepared through the concise intramolecular double Friedel–Crafts acylation strategy.
Palladium-catalysed regioselective hydroamination of 1,3-dienes: synthesis of allylic amines
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.
Sterically demanding aryl–alkyl Suzuki–Miyaura coupling
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.
Synthesis of β-methyl-α-methylene-γ-butyrolactone from biorenewable itaconic acid
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.
Copper-catalyzed three-component synthesis of 5-acetamidoimidazoles from carbodiimides, acyl chlorides and isocyanides
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.
Highly selective 4-alkynoic acids synthesis via iron-mediated complete inversion of stereogenic carbon centers
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.
Solvent-driven selective π-cation templating in dynamic assembly of interlocked molecules
The different solvent responses for bipyridinium and trispyridinium-based dynamic imine rotaxanes allow their interconversion with high selectivity.
Highly diasteroselective intermolecular 1,3-dipolar cycloaddition reactions of carbonyl ylides with aldimines to afford sterically disfavored cis-oxazolidines
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.
Palladium-catalyzed base-accelerated direct C–H bond alkenylation of phenols to synthesize coumarin derivatives
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, room-temperature radical azidofluorination of unactivated alkenes in aqueous solution
Transition-metal-free radical azidofluorination of unactivated alkenes was successfully achieved in aqueous solution at room temperature with excellent regioselectivity and functional group compatibility.
About this collection
Read some of the best research published by Organic Chemistry Frontiers in 2014. These articles are recommended by OCF referees as being of significant novelty and interest.