Themed collection HOT articles in Organic Chemistry Frontiers in 2016
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Synthesis of a figure-eight azahelicene dimer with high emission and CPL properties
A bisbutadiyne bridged azahelicene dimer with a figure-eight shape, which exhibited both high fluorescence quantum yield and CPL properties, has been synthesized through the Glaser–Hay homo-coupling reaction with diethynylazahelicene.
Org. Chem. Front., 2017,4, 664-667
https://doi.org/10.1039/C6QO00629A
Mechanism of selective C–H cyanation of 2-phenylpyridine with benzyl nitrile catalyzed by CuBr: a DFT investigation
The mechanism of C–H cyanation of 2-phenylpyridine with 2-phenylacetonitrile catalyzed by the CuBr catalyst was elaborated based on DFT calculations.
Org. Chem. Front., 2017,4, 377-385
https://doi.org/10.1039/C6QO00652C
New reactivity of ethynyl benziodoxolone: modulating iron-catalyzed dehydration of propargyl alcohols
This is the first example of using only a catalytic amount of silyl-EBX in a dehydration reaction since its discovery. Preliminary mechanistic studies ruled out the radical pathways and supported an E1 process.
Org. Chem. Front., 2017,4, 409-412
https://doi.org/10.1039/C6QO00631K
The stability and reactivity of tri-, di-, and monofluoromethyl/methoxy/methylthio groups on arenes under acidic and basic conditions
The stability and reactivity of tri-, di- and monofluoromethyl groups under acidic and basic conditions are described.
Org. Chem. Front., 2017,4, 214-223
https://doi.org/10.1039/C6QO00674D
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Direct observation and characterisation of 3-azido-2H-azirines: postulated, but highly elusive intermediates
The title compounds, including the parent 3-azido-2H-azirine, were generated by low-temperature photolysis of the corresponding 1,1-diazidoethenes, and characterised not only by trapping reactions, but also by direct detection using NMR and in situ IR spectroscopy.
Org. Chem. Front., 2017,4, 191-195
https://doi.org/10.1039/C6QO00625F
Copper-mediated annulation of 2-(1-arylvinyl) anilines and aryl nitrosos towards 2,3-diaryl-2H-indazoles
A copper-mediated annulation of 2-(1-substituted vinyl)anilines and aryl nitrosos is developed, giving 2,3-diaryl pyrazoles in moderate to good yields.
Org. Chem. Front., 2017,4, 22-25
https://doi.org/10.1039/C6QO00540C
The facile and stereoselective synthesis of pyrrolidine β-amino acids via copper(I)-catalyzed asymmetric 1,3-dipolar cycloaddition
A highly efficient copper(I)-catalyzed asymmetric 1,3-dipolar cycloaddition was developed, which provides a straightforward and efficient pathway to highly functionalized free pyrrolidine β-amino acids.
Org. Chem. Front., 2017,4, 52-56
https://doi.org/10.1039/C6QO00512H
Suzuki coupling for preparation of allenes – ligand effects and chirality transfer
o-(Diphenylphosphino)benzaldehyde has been identified as the effective ligand for the coupling of propargylic carbonates and organoboronic acids under mild conditions.
Org. Chem. Front., 2016,3, 1705-1710
https://doi.org/10.1039/C6QO00489J
Rh(I)-Catalyzed coupling of 2-bromoethyl aryldiazoacetates with tertiary propargyl alcohols through carbene migratory insertion
A Rh(I)-catalyzed cross-coupling of 2-bromoethyl aryldiazoacetates with tertiary propargyl alcohols has been successfully achieved.
Org. Chem. Front., 2016,3, 1691-1698
https://doi.org/10.1039/C6QO00453A
[2.2]Paracyclophane-based N-heterocyclic carbene as efficient catalyst or as ligand for copper catalyst for asymmetric α-silylation of N-tosylaldimines
A carbene precursor plays a dual role as both an organocatalyst and as a ligand for the copper catalyst in asymmetric silylation.
Org. Chem. Front., 2016,3, 1725-1737
https://doi.org/10.1039/C6QO00386A
Manganese-catalysed hydroperoxidation of carbon–carbon double bonds using molecular oxygen present in air and hydroxylamine under ambient conditions
A highly efficient manganese-catalysed hydroperoxidation of carbon–carbon double bonds of enynes as well as styrene derivatives using N-hydroxyphthalimide, N-hydroxybenzotriazole or N-hydroxysuccinimide was developed.
Org. Chem. Front., 2016,3, 1420-1424
https://doi.org/10.1039/C6QO00318D
A new approach toward the synthesis of 2,4-bis(fluoroalkyl)-substituted quinoline derivatives using fluoroalkyl amino reagent chemistry
The present work describes the unprecedented use of Fluoroalkyl Amino Reagents (FARs) to afford 2,4-bis(fluoroalkyl)-substituted quinoline derivatives in two steps under mild reaction conditions, in good yields and with a very good regioselectivity.
Org. Chem. Front., 2016,3, 1392-1415
https://doi.org/10.1039/C6QO00319B
Iterative catalyst controlled diastereodivergent synthesis of polypropionates
Polypropionates are synthesized using a combination of a copper-catalyzed asymmetric allylic alkylation, ruthenium-catalyzed cross-metathesis and iridium-catalyzed asymmetric allylic etherification.
Org. Chem. Front., 2016,3, 1383-1391
https://doi.org/10.1039/C6QO00199H
Synthesis of 2,3-dihydrobenzofurans via the palladium catalyzed carboalkoxylation of 2-allylphenols
A new Pd-catalyzed alkene carboalkoxylation strategy for the preparation of 2,3-dihydrobenzofurans is described.
Org. Chem. Front., 2016,3, 1314-1318
https://doi.org/10.1039/C6QO00215C
Switching between intermolecular and intramolecular reactions using flow microreactors: lithiation of 2-bromo-2′-silylbiphenyls
Switching between the intermolecular reaction and the intramolecular reaction was achieved at will using flow microreactors.
Org. Chem. Front., 2016,3, 1250-1253
https://doi.org/10.1039/C6QO00257A
Considering organic mechanisms and the optimization of current flow in an electrochemical oxidative condensation reaction
Careful consideration of the chemical mechanism for an oxidative condensation reaction led to improved current flow for the electrolysis.
Org. Chem. Front., 2016,3, 1236-1240
https://doi.org/10.1039/C6QO00248J
Catalytic asymmetric direct-type 1,4-addition reactions of simple esters
Catalytic asymmetric 1,4-addition reactions of simple esters have been developed. The desired reactions proceeded smoothly with high enantioselectivities.
Org. Chem. Front., 2016,3, 1241-1245
https://doi.org/10.1039/C6QO00242K
Rhodium/copper-cocatalyzed annulation of benzylamines with diazo compounds: access to fused isoquinolines
Benzylamines undergo C–H activation and aerobic coupling with diazo compounds, leading to the synthesis of fused isoquinolines. This occurs via a mild synergistic rhodium- and copper-catalyzed process.
Org. Chem. Front., 2016,3, 1159-1162
https://doi.org/10.1039/C6QO00287K
Hyperbranched supramolecular polymer constructed from twisted cucurbit[14]uril and porphyrin via host–guest interactions
A novel supramolecular polymer was constructed between Q[14] host and 5,10,15,20-tetrakis(N-butyl-4-pyridinium)porphyrin tetrabromide guest depending on the host–guest interactions, representing the first cucurbit[14]uril-involved host–guest supramolecular polymer.
Org. Chem. Front., 2016,3, 1144-1148
https://doi.org/10.1039/C6QO00310A
Approach to the synthesis of the C1–C11 and C14–C18 portion of Leucascandrolide A
An iterative asymmetric hydration of dienoates approach to Leucasndrolide A was explored.
Org. Chem. Front., 2016,3, 1120-1125
https://doi.org/10.1039/C6QO00284F
Pd(II)-catalyzed direct functionalization of C–H bonds of benzamides for synthesis of 1,1-difluoro-1-alkenes
Pd-catalyzed difluoroallylation of unactivated C(sp2)–H bonds with readily available Rf-Br reagents is described.
Org. Chem. Front., 2016,3, 1080-1083
https://doi.org/10.1039/C6QO00178E
Bismuth(III) triflate-catalysed tandem cyclisations towards complex polycyclic ethers
A series of complex polycyclic ethers have been synthesised under very mild conditions using a low catalyst loading of bismuth(III) triflate.
Org. Chem. Front., 2016,3, 999-1003
https://doi.org/10.1039/C6QO00212A
Reaction of alkenecarboxylic acids with isocyanates via rhodium(III)-catalyzed C–H activation: a versatile route to cyclic imides
A versatile cascade route to cyclic imides via direct functionalization of the β-alkenyl C–H bond of alkenoic acids was developed.
Org. Chem. Front., 2016,3, 971-974
https://doi.org/10.1039/C6QO00119J
Stimuli-responsive supramolecular gel constructed by pillar[5]arene-based pseudo[2]rotaxanes via orthogonal metal–ligand coordination and hydrogen bonding interaction
A supramolecular polyrotaxane constructed by pillar[5]arene-based pseudo[2]rotaxanes via the incorporation of metal–ligand coordination could further self-assemble to form a stimuli-responsive supramolecular gel at high concentration.
Org. Chem. Front., 2016,3, 966-970
https://doi.org/10.1039/C6QO00197A
Synthesis of trifluoromethylthiolated azacalix[1]arene[3]pyridines from the Cu(II)-mediated direct trifluoromethylthiolation reaction of arenes via reactive arylcopper(III) intermediates
Cu(II)-mediated arene C–H bond trifluoromethylthiolation with Me4NSCF3 proceeds via arylcopper(III) intermediates to produce functionalized azacalix[1]arene[3]pyridine macrocycles.
Org. Chem. Front., 2016,3, 880-886
https://doi.org/10.1039/C6QO00161K
Metal-free borylation of electron-rich aryl (pseudo)halides under continuous-flow photolytic conditions
A photochemical borylation of electron-rich aryl (pseudo)halides via a triplet aryl cation mechanism has been described.
Org. Chem. Front., 2016,3, 875-879
https://doi.org/10.1039/C6QO00109B
Synthesis of 2,5-disubstituted pyrroles via dehydrogenative condensation of secondary alcohols and 1,2-amino alcohols by supported platinum catalysts
2,5-Disubstituted pyrroles are synthesized by acceptorless dehydrogenative reaction of 1,2-aminoalcohols and secondary alcohols by Pt/carbon catalyst.
Org. Chem. Front., 2016,3, 846-851
https://doi.org/10.1039/C6QO00165C
A general photoinduced electron transfer-directed chemoselective perfluoroalkylation of N,N-dialkylhydrazones
The first metal-free, initiator-free, and general photochemical perfluoroalkylation of a variety of N,N-dialkylhydrazones was developed at room temperature in the absence of any external photocatalyst.
Org. Chem. Front., 2016,3, 841-845
https://doi.org/10.1039/C6QO00158K
Catalytic asymmetric α-amination of β-keto esters and β-keto amides with a chiral N,N′-dioxide–copper(I) complex
The highly efficient asymmetric α-amination of β-keto esters and β-keto amides was realized by using a chiral N,N′-dioxide/Cu(I) complex. Under mild reaction conditions, a series of chiral α-amino dicarbonyl compounds were obtained in good result.
Org. Chem. Front., 2016,3, 809-812
https://doi.org/10.1039/C6QO00095A
Enantioselective gold-catalyzed intermolecular [2 + 2]-cycloadditions of 3-styrylindoles with N-allenyl oxazolidinone
A series of novel chiral monophosphine ligands Xiang-Phoses were designed and have been applied to the enantioselective gold-catalyzed intermolecular [2 + 2]-cycloaddition of 3-styrylindoles 1 with N-allenyl oxazolidinone 2.
Org. Chem. Front., 2016,3, 759-763
https://doi.org/10.1039/C6QO00087H
Synthesis of carbamates from amines and N-tosylhydrazones under atmospheric pressure of carbon dioxide without an external base
A synthetic method to carbamates from amines and N-tosylhydrazones in the presence of 1 atm of carbon dioxide was developed.
Org. Chem. Front., 2016,3, 764-767
https://doi.org/10.1039/C6QO00111D
Copper(I)-catalyzed sulfonylation of (2-alkynylaryl)boronic acids with DABSO
The scaffold of benzo[b]thiophene 1,1-dioxides can be easily constructed through a copper(I)-catalyzed insertion of sulfur dioxide into (2-alkynylaryl)boronic acids. The reaction proceeds via insertion of sulfur dioxide and subsequent intramolecular 5-endo cyclization.
Org. Chem. Front., 2016,3, 693-696
https://doi.org/10.1039/C6QO00070C
Generation of N-aminosulfonamides via a photo-induced fixation of sulfur dioxide into aryl/alkyl halides
A catalyst-free aminosulfonylation through insertion of sulfur dioxide with aryl/alkyl halides enabled by photoenergy is presented. Under ultraviolet irradiation, a three-component reaction of aryl/alkyl halides, sulfur dioxide, and hydrazines proceeds under mild conditions without any metals or photo-redox catalysts.
Org. Chem. Front., 2016,3, 574-578
https://doi.org/10.1039/C6QO00060F
Epoxy and aziridinyl enolsilanes in diastereoselective inter- and intramolecular Friedel–Crafts alkylations
Diastereoselective Friedel–Crafts reactions of optically pure epoxy enolsilanes afford enantiomerically-enriched β-hydroxy-α-arylketones. Aziridinyl enolsilanes react in an analogous manner.
Org. Chem. Front., 2016,3, 457-461
https://doi.org/10.1039/C5QO00333D
Visible-light promoted intermolecular halofunctionalization of alkenes with N-halogen saccharins
A simple and efficient visible-light promoted intermolecular haloamination and haloetherification of alkenes was reported.
Org. Chem. Front., 2016,3, 447-452
https://doi.org/10.1039/C5QO00432B
Pd(II)-catalyzed β-C–H arylation of O-methyl ketoximes with iodoarenes
A Pd(II)-catalyzed selective β-arylation of O-methyl ketoximes was developed using iodoarenes as the coupling partners.
Org. Chem. Front., 2016,3, 380-384
https://doi.org/10.1039/C5QO00438A
Gold-catalyzed tandem synthesis of bioactive spiro-dipyrroloquinolines and its application in the one-step synthesis of incargranine B aglycone and seneciobipyrrolidine (I)
The Au-catalyzed tandem reaction provided simple and efficient access to spiro-dipyrroloquinolines and incargranine B aglycone and (±)-seneciobipyrrolidine (I).
Org. Chem. Front., 2016,3, 324-329
https://doi.org/10.1039/C5QO00354G
Pd/norbornene-catalyzed sequential ortho-C–H alkylation and ipso-alkynylation: a 1,1-dimethyl-2-alkynol strategy
A palladium/norbornene-catalyzed ortho-C–H alkylation and ipso-alkynylation reaction for the synthesis of 2-alkyl-1-alkynyl arenes was reported, where the use of bulky 1,1-dimethyl-2-alkynols led to significant suppression of the formation of O-alkylation and norbornene alkynylation by-products.
Org. Chem. Front., 2016,3, 309-313
https://doi.org/10.1039/C5QO00391A
Access to bicyclic hydroxamate macrocycles via intramolecular aza-(4 + 3) cyloaddition reactions of aza-oxyallylic cation intermediates
The intramolecular aza-(4 + 3) cycloaddition reactions of in situ generated aza-oxyallylic cations and furans have been reported for the construction of medium sized hydroxamate macrocycles.
Org. Chem. Front., 2016,3, 330-334
https://doi.org/10.1039/C5QO00315F
Exploiting ortho-substitution effect on formation of oxygen-containing [10]paracyclophane through ring-closing metathesis
The synthesis of strained paracyclophanes is facilitated by ortho-substitution effect on phenyl ring.
Org. Chem. Front., 2016,3, 319-323
https://doi.org/10.1039/C5QO00373C
About this collection
Read some of the best research published by Organic Chemistry Frontiers in 2016. These articles are recommended by OCF referees as being of significant novelty and interest.