Themed collection HOT articles in Organic Chemistry Frontiers in 2015
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Regioselective palladium(II)-catalyzed aerobic oxidative Heck-type C3 alkenylation of sulfocoumarins
An efficient method for the direct C–H olefination of sulfocoumarins with a wide range of alkenes is developed. Moreover, O2 was successfully utilized as the sole oxidant for the oxidative Heck reaction. This approach enables the rapid generation of various 3-alkenylated sulfocoumarins.
Org. Chem. Front., 2015,2, 1621-1624
https://doi.org/10.1039/C5QO00294J
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Rhodium catalysed conversion of carbenes into ketenes and ketene imines using PNN pincer complexes
PNN pincer-type rhodium complexes catalyze ketene and ketene imine synthesis, using CO or an isocyanide and a carbene precursor.
Org. Chem. Front., 2015,2, 1561-1577
https://doi.org/10.1039/C5QO00287G
Direct borylation of benzyl alcohol and its analogues in the absence of bases
Direct borylation of arylmethanols to synthesize important and useful benzylboronates was carried out through Pd(OAc)2-catalyzed sp3 C–O activation.
Org. Chem. Front., 2015,2, 1505-1510
https://doi.org/10.1039/C5QO00243E
Stereoselective formation of chiral trans-4-hydroxy-5-substituted 2-pyrrolidinones: syntheses of streptopyrrolidine and 3-epi-epohelmin A
A highly diastereoselective approach for synthesis of trans-4-hydroxy-5-substituted 2-pyrrolidinones has been developed. The streptopyrrolidine and 3-epi-epohelmin A were synthesized by this one-pot cascade protocol.
Org. Chem. Front., 2015,2, 1485-1499
https://doi.org/10.1039/C5QO00250H
Silver-catalyzed [3 + 2] cycloaddition of isocyanides with diazo compounds: new regioselective access to 1,4-disubstituted-1,2,3-triazoles
An unprecedented silver-catalyzed 1,3-dipolar cycloaddition reaction of isocyanides with diazo compounds to afford 1,4-disubstituted 1,2,3-triazoles is realized.
Org. Chem. Front., 2015,2, 1468-1474
https://doi.org/10.1039/C5QO00219B
Speciation and kinetic study of iron promoted sugar conversion to 5-hydroxymethylfurfural (HMF) and levulinic acid (LA)
Identification of catalytic species and their contributions in iron catalyzed sugar conversion to hydroxymethylfurfural and levulinic acid.
Org. Chem. Front., 2015,2, 1388-1396
https://doi.org/10.1039/C5QO00194C
Palladium-catalyzed methylene C(sp3)–H arylation of the adamantyl scaffold
A palladium-catalyzed C(sp3)–H arylation of adamantane at the methylene position with the assistance of an amide group was developed.
Org. Chem. Front., 2015,2, 1374-1378
https://doi.org/10.1039/C5QO00218D
Cu-Mediated 2,2,2-trifluoroethylation of terminal alkynes using 1,1-dichloro-2,2,2-trifluoroethane (HCFC-123)
Cu-Promoted coupling reactions of HCFC-123 with terminal alkynes give trifluoroethylated internal alkynes.
Org. Chem. Front., 2015,2, 1379-1387
https://doi.org/10.1039/C5QO00210A
Efficient synthesis of P-chiral biaryl phosphonates by stereoselective intramolecular cyclization
A series of P-chiral biaryl phosphonates were efficiently synthesized from diaryl 2-bromo arylphosphonates in high yields (up to 92%) and good enantioselectivities (up to 88% ee) through a palladium-catalyzed desymmetric intramolecular cyclization with a P-chiral biaryl monophosphorus ligand.
Org. Chem. Front., 2015,2, 1342-1345
https://doi.org/10.1039/C5QO00142K
Organoselenium-catalyzed synthesis of indoles through intramolecular C–H amination
An efficient approach for organoselenium-catalyzed synthesis of indoles via intramolecular C–H amination has been developed.
Org. Chem. Front., 2015,2, 1334-1337
https://doi.org/10.1039/C5QO00179J
A thermally stable pH-responsive “supramolecular buckle” based on the encapsulation of 4-(4-aminophenyl)-N-methylpyridinium by cucurbit[8]uril
A CB[8]-based host-guest system forms a thermally stable 1 : 2 complex under neutral conditions and transforms into a 1 : 1 complex upon acidification, which makes it a “supramolecular buckle” to fabricate pH-responsive materials at elevated temperatures.
Org. Chem. Front., 2015,2, 1030-1034
https://doi.org/10.1039/C5QO00168D
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Intramolecular C–H insertion vs. Friedel–Crafts coupling induced by silyl cation-promoted C–F activation
Silyl cation-promoted aryl C–F activation can lead to formal C–H activation and the formation of new C(ar)–C(alkyl) bonds.
Org. Chem. Front., 2015,2, 1018-1021
https://doi.org/10.1039/C5QO00170F
Copper-mediated oxidative difluoromethylation of terminal alkynes with TMSCF2H
A copper-mediated oxidative coupling of terminal alkynes and TMSCF2H has been described for the preparation of various difluoromethylated alkynes.
Org. Chem. Front., 2015,2, 1022-1025
https://doi.org/10.1039/C5QO00186B
A novel dynamic pseudo[1]rotaxane based on a mono-biotin-functionalized pillar[5]arene
A stable pillar[5]arene-based pseudo[1]rotaxane P1′ was synthesized by the click reaction, which exhibited a dynamic slow disassembly process upon adding a strong-polar solvent or competitive guest. Moreover, this dynamic behavior might be used as a switch to turn on or off the bioactivity of the biotin moiety in aqueous solution.
Org. Chem. Front., 2015,2, 1013-1017
https://doi.org/10.1039/C5QO00159E
Syntheses of sceptrins and nakamuric acid and insights into the biosyntheses of pyrrole–imidazole dimers
The SET-promoted homodimerization of pyrrole–imidazole alkaloids is a stepwise reaction favoring the [2 + 2] pathway.
Org. Chem. Front., 2015,2, 978-984
https://doi.org/10.1039/C5QO00165J
Sulfone promoted Rh(III)-catalyzed C–H activation and base assisted 1,5-H shift strategy for the construction of seven-membered rings
A sequence of Rh(III)-catalyzed C–H cleavage, 1,5-H shift and intramolecular allene insertion was developed for the construction of seven-membered rings.
Org. Chem. Front., 2015,2, 947-950
https://doi.org/10.1039/C5QO00089K
Catalytic enantioselective synthesis of quaternary 3,3′-indolyloxindoles by combination of Rh(II) complexes and chiral phosphines
Rh(II)/chiral phosphine combined catalysis has been developed for a highly efficient sequential C–H functionalization/asymmetric allylation or Michael addition reaction to afford a diverse range of quaternary 3,3′-indolyloxindole derivatives.
Org. Chem. Front., 2015,2, 956-960
https://doi.org/10.1039/C5QO00151J
Palladium-catalyzed direct ortho C–O bond construction of azoxybenzenes with carboxylic acids and alcohols
A Pd(II) catalyzed C–O bond formation of azoxybenzenes has been developed.
Org. Chem. Front., 2015,2, 951-955
https://doi.org/10.1039/C5QO00120J
Formal synthesis of (−)-platensimycin
An efficient formal synthesis of (−)-platensimycin was completed by using a tandem C–H oxidation/C–C coupling (cyclization)/rearrangement as the key step.
Org. Chem. Front., 2015,2, 913-916
https://doi.org/10.1039/C5QO00109A
Palladium-catalyzed intramolecular rearrangement of vinylidenecyclopropanes through C–C bond activation
An intramolecular rearrangement of vinylidenecyclopropanes to dimethylenecyclopropanes through C–C bond activation has been developed.
Org. Chem. Front., 2015,2, 792-796
https://doi.org/10.1039/C5QO00127G
Mechanistic studies on C–C reductive coupling of five-coordinate Rh(III) complexes
C–C reductive coupling of rare five-coordinate rhodium(III) complexes has been studied in detail.
Org. Chem. Front., 2015,2, 783-791
https://doi.org/10.1039/C5QO00049A
Pd-catalyzed Heck cyclization and in situ hydrocarboxylation or hydromethenylation via a hydrogen borrowing strategy
A palladium-catalyzed Heck cyclization and in situ hydrocarboxylation reaction was developed using chloroform as a one-carbon elongation reagent.
Org. Chem. Front., 2015,2, 778-782
https://doi.org/10.1039/C5QO00091B
Ruthenium-catalyzed alkoxycarbonylation of alkenes using carbon monoxide
The first ruthenium-catalyzed alkoxycarbonylation of alkenes with alcohols using carbon monoxide as carbonyl source is realized.
Org. Chem. Front., 2015,2, 771-774
https://doi.org/10.1039/C5QO00071H
A challenging Heck reaction of maleimides
A difficult Heck reaction of base-sensitive maleimides is realized by using a weak base in a carbonate solvent.
Org. Chem. Front., 2015,2, 775-777
https://doi.org/10.1039/C5QO00015G
Sulfur-containing stable five-membered “cycloallene” complexes: 1-thia-2-zircona- and 1-thia-2-titanacyclopenta-3,4-dienes
Stable five-membered sulfur-containing metallacyclic allenes, 1-thia-2-metallacyclopenta-3,4-diene, were synthesized from the reactions of low-valent zirconocene or titanocene with alkynylthioamides.
Org. Chem. Front., 2015,2, 681-687
https://doi.org/10.1039/C5QO00072F
Highly efficient and practical hydrogenation of olefins catalyzed by in situ generated iron complex catalysts
In situ generated Fe catalysts from bench-stable Fe(II) complexes and LiAlH4 exhibited unprecedented activity for the hydrogenation of olefins.
Org. Chem. Front., 2015,2, 692-696
https://doi.org/10.1039/C5QO00064E
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A one-pot dilithiation–lithium–zinc exchange–Negishi coupling approach to 2,6-di(hetero)aryl substituted dithienothiazines – a novel class of electronically fine-tunable redox systems
2,6-Di(hetero)aryl substituted dithienothiazines with fine-tunable electronic properties are efficiently accessible by lithiation–lithium–zinc exchange–Negishi cross-coupling in a one-pot fashion.
Org. Chem. Front., 2015,2, 481-491
https://doi.org/10.1039/C5QO00046G
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Regio- and stereoselective synthesis of α-hydroxy-β-azido tetrazoles
Unreported α-hydroxy-β-azido tetrazoles are prepared in a single step and mild conditions from readily available epoxy nitriles.
Org. Chem. Front., 2015,2, 492-496
https://doi.org/10.1039/C4QO00345D
New building blocks for iminosugars: a concise synthesis of polyhydroxylated N-alkoxypiperidines through an intramolecular azepine ring contraction
Polyhydroxylated piperidines are a functionally rich class of biologically active molecules that have broad therapeutic potential.
Org. Chem. Front., 2015,2, 497-501
https://doi.org/10.1039/C4QO00330F
Meinwald-type rearrangement of monosubstituted epoxides to methyl ketones using an [Al porphyrin]+[Co(CO)4]− catalyst
A Meinwald-type rearrangement of monosubstituted epoxides to methyl ketones using a well-defined aluminum porphyrin catalyst is reported.
Org. Chem. Front., 2015,2, 346-349
https://doi.org/10.1039/C4QO00324A
Pd(II)-catalyzed asymmetric addition of arylboronic acids to cyclic N-sulfonyl ketimine esters and a DFT study of its mechanism
A highly efficient palladium-catalyzed asymmetric arylation of cyclic ketimine esters is developed, which provides the desired product in up to 99% yield with up to 99% ee. The mechanism of enantioselection is studied using DFT calculation.
Org. Chem. Front., 2015,2, 398-402
https://doi.org/10.1039/C4QO00347K
TEMP and copper cocatalyzed oxygenation of ketones with molecular oxygen: chemoselective synthesis of α-ketoesters
A practical approach to α-ketoesters through TEMP and copper cocatalyzed chemoselective oxidative coupling of methyl ketones with alcohols is developed.
Org. Chem. Front., 2015,2, 354-359
https://doi.org/10.1039/C5QO00028A
Alkyl- and aryl-thioalkylation of olefins with organotrifluoroborates by photoredox catalysis
A new photocatalytic alkyl- and aryl-thioalkylation of electron-deficient olefins using organotrifluoroborates has been developed.
Org. Chem. Front., 2015,2, 319-323
https://doi.org/10.1039/C4QO00352G
Au(I) π-bis(tert-butyldimethylsilyl)acetylene triphenylphosphine complex, an effective pre-catalyst for Au(I)-catalyzed reactions
A [Ph3PAu]+ η2-alkyne π complex is found to be shelf-stable and effective for a range of the Au(I)-catalyzed alkyne π activation reactions.
Org. Chem. Front., 2015,2, 360-365
https://doi.org/10.1039/C5QO00023H
Phase-transfer-catalyzed asymmetric desymmetrizations of cyclopentanones
Highly enantioselective phase-transfer-catalyzed epoxide-opening reaction and isomerization of cyclopentanones were achieved.
Org. Chem. Front., 2015,2, 336-339
https://doi.org/10.1039/C4QO00339J
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Selective syntheses of leuconolam, leuconoxine, and mersicarpine alkaloids from a common intermediate through regiocontrolled cyclizations by Staudinger reactions
Selective syntheses of alkaloids bearing distinct core structures were enabled by chemically programmed polycyclizations using water as a switch.
Org. Chem. Front., 2015,2, 236-240
https://doi.org/10.1039/C4QO00312H
Indolizine synthesis via Cu-catalyzed cyclization of 2-(2-enynyl)pyridines with nucleophiles
Cu-catalyzed cyclization of 2-(2-enynyl)pyridines with various nucleophiles was developed, providing efficient access to indolizine derivatives.
Org. Chem. Front., 2015,2, 226-230
https://doi.org/10.1039/C4QO00336E
Gold(I)-catalyzed asymmetric [3 + 2]-cycloadditions of γ-1-ethoxyethoxy-propiolates and aldehydes
A gold-catalyzed asymmetric intermolecular [3 + 2]-cycloaddition of γ-1-ethoxyethoxy-propiolate and aldehydes by using the chiral ligand 5a or 5b is developed, which provides facile access to highly substituted 2,5-dihydrofurans in up to 84% yield with up to 97% ee.
Org. Chem. Front., 2015,2, 221-225
https://doi.org/10.1039/C4QO00261J
N-heterocyclic carbene-based ruthenium-catalyzed direct amidation of aldehydes with amines
Ru-catalyzed dehydrogenative amide synthesis from aldehydes and amines was achieved, based on the idea of using a hemiaminal intermediate to generate the active Ru-hydride species.
Org. Chem. Front., 2015,2, 241-247
https://doi.org/10.1039/C4QO00319E
Simple, versatile, and chemoselective reduction of secondary amides and lactams to amines with the Tf2O–NaBH4 or Cp2ZrHCl–NaBH4 system
A convenient method for the direct reduction of secondary amides and lactams to amines is reported.
Org. Chem. Front., 2015,2, 150-158
https://doi.org/10.1039/C4QO00317A
Cationic Pd(II)-catalyzed cyclization of N-tosyl-aniline tethered alkynyl ketones initiated by hydropalladation of alkynes: a facile way to 1,2-dihydro or 1,2,3,4-tetrahydroquinoline derivatives
A cationic Pd(II)-catalyzed intramolecular alkyne-carbonyl reductive coupling reaction of N-tosyl-aniline tethered alkynyl ketones under transfer hydrogenation conditions to give hydroquinolines is developed.
Org. Chem. Front., 2015,2, 145-149
https://doi.org/10.1039/C4QO00286E
Cu- or Fe-catalyzed C–H/C–C bond nitrogenation reactions for the direct synthesis of N-containing compounds
This tutorial account summarizes the recent progress in Cu- or Fe-catalyzed C–H/C–C bond nitrogenation reactions for the direct synthesis of N-containing compounds.
Org. Chem. Front., 2015,2, 403-415
https://doi.org/10.1039/C4QO00350K
Catalytic dehydrogenative aromatization: an alternative route to functionalized arenes
Catalytic dehydrogenative aromatization has emerged as an efficient and environmentally friendly way to access functionalized arenes in recent years.
Org. Chem. Front., 2015,2, 279-287
https://doi.org/10.1039/C4QO00358F
Difluoromethyl 2-pyridyl sulfone: a versatile carbonyl gem-difluoroolefination reagent
The gem-difluoroolefination of carbonyl compounds with difluoromethyl 2-pyridyl sulfone (2-PySO2CF2H) has been summarized in this tutorial account.
Org. Chem. Front., 2015,2, 163-168
https://doi.org/10.1039/C4QO00291A
About this collection
Read some of the best research published by Organic Chemistry Frontiers in 2015. These articles are recommended by OCF referees as being of significant novelty and interest.