Themed collection Organic Chemistry Frontiers HOT articles for 2017
Visible-light-induced tandem phosphorylation cyclization of vinyl azides under mild conditions
This method provides a visible-light-induced radical tandem cyclization for the synthesis of phosphorus phenanthridines with various nitrogen-containing substrates.
The hexameric resorcinarene capsule as an artificial enzyme: ruling the regio and stereochemistry of a 1,3-dipolar cycloaddition between nitrones and unsaturated aldehydes
The hexameric resorcinarene capsule as an artificial enzyme to rule the regio and stereochemistry of a 1,3-dipolar cycloaddition.
Synthesis of pyridine trans-tetrafluoro-λ6-sulfane derivatives via radical addition
Pyridine-trans-SF4-alkenes or -alkanes have been synthesized for the first time via the radical addition reactions of pyridine-trans-SF4Cl to alkynes or alkenes in good to high yields.
Thiazolium salt-catalyzed [3 + 2 + 1] cyclization for the synthesis of trisubstituted 2-pyrones using arylglyoxals as a carbonyl source
A new thiazolium salt-catalyzed [3 + 2 + 1] cyclization of acetylenedicarboxylates with arylglyoxals has been developed, enabling organocatalytic umpolung to access trisubstituted 2-pyrones with good yields via C–C bond cleavage.
Enantioselective palladium-catalyzed C–H functionalization of pyrroles using an axially chiral 2,2′-bipyridine ligand
An enantioselective palladium-catalyzed C–H functionalization of pyrroles with diazoacetates has been developed with up to 90% of enantioselectivity.
Nickel-catalyzed direct difluoromethylation of aryl boronic acids with BrCF2H
Nickel-catalyzed direct difluoromethylation of aryl boronic acids has been developed with the industrial raw material BrCF2H.
An effective approach to aryl-substituted propanoic acids via the Pd-catalyzed hydrocarboxylation of stilbenes
An effective Pd(0)-catalyzed hydrocarboxylation of substituted stilbenes with formic acid and HCOOPh is described. A variety of aryl-substituted propanoic acids are obtained in good yields without using external toxic CO gas.
A copper-catalyzed sulfonylative C–H bond functionalization from sulfur dioxide and aryldiazonium tetrafluoroborates
Sulfonylative C–H bond functionalization through a copper-catalyzed three-component reaction of 8-aminoquinoline amides, DABCO·(SO2)2 and aryldiazonium tetrafluoroborates is developed. Excellent selectivity in the para-position is observed.
Facile synthesis of carbo- and heterocycles via Fe(III)-catalyzed alkene hydrofunctionalization
A facile synthesis of carbo- and heterocycles via Fe(III)-catalyzed alkene hydrofunctionalization has been developed.
Regioselective C5 alkenylation of 2-acylpyrroles via Pd(II)-catalyzed C–H bond activation
A Pd(II)-catalyzed regioselective C5 alkenylation of 2-acylpyrroles to synthesize various C5-alkenylated 2-acylpyrroles using a readily removable N-protecting group is developed.
A copper(I)-catalyzed asymmetric Mannich reaction of glycine Schiff bases with isatin-derived ketimines: enantioselective synthesis of 3-substituted 3-aminooxindoles
We have developed a copper/Ph-Phosferrox-catalyzed asymmetric Mannich reaction of Schiff bases with isatin-derived ketimines to prepare 3-substituted 3-aminooxindoles with excellent results.
Scandium-catalyzed C(sp3)–H alkylation of N,N-dimethyl anilines with alkenes
A scandium complex enabled an atom- and step-economical C(sp3)–H addition of N,N-dimethyl anilines to a variety of unactivated alkenes affording branched products.
Rearranged limonoids with unique 6/5/6/5 tetracarbocyclic skeletons from Toona ciliata and biomimetic structure divergence
Rearranged limonoids with 6/5/6/5 carbon skeletons, were characterized as metabolite and biomimetic products.
Gold-catalyzed diversified synthesis of 3-aminosugar analogues of digitoxin and digoxin
A small library containing 3-aminosugar analogues of digitoxin and digoxin with potent anticancer activities was constructed by gold-catalyzed glycosylation.
A redox-responsive supramolecular amphiphile fabricated by selenium-containing pillararene-based host–guest recognition
A novel redox-responsive molecular recognition motif was built between a neutral selenium-containing pillararene and a pyridinium bromide salt in water. It was further used to construct the first pillararene-based selenium-containing supramolecular amphiphile with application in controlled release.
Harnessing the potential diversity of resinic diterpenes through visible light-induced sensitized oxygenation coupled to Kornblum–DeLaMare and Hock reactions
A biomimetic procedure for the late functionalization of resinic acids is reported, implementing photooxygenation by singlet oxygen, using visible light and a photosensitized, combined to the Kornblum–DeLaMare reaction or the Hock rearrangement.
Tunable regiodivergent phosphine-catalyzed [3 + 2] cycloaddition of alkynones and trifluoroacetyl phenylamides
The regiodivergent phosphine-catalyzed [3 + 2] cycloaddition of 2-(2,2,2-trifluoroacetyl)phenylamides and alkynones have been achieved through adjusting the acidities of substrates, changing reaction temperature and addition of protic additive H2O. The detailed mechanism was systematically studied.
Comparative investigation of the reactivities between catalysts [Cp*RhCl2]2 and [Cp*IrCl2]2 in the oxidative annulation of isoquinolones with alkynes: a combined experimental and computational study
The origin of the lower reactivity of [Cp*IrCl2]2 relative to [Cp*RhCl2]2 is disclosed and the substituent effects on reactivities are discussed.
Photoredox meets gold Lewis acid catalysis in the alkylative semipinacol rearrangement: a photocatalyst with a dark side
The alkylative semipinacol rearrangement of a variety of TMS protected α-styrenyl substituted cyclic alcohols with unactivated bromoalkanes that merge photoredox and Au(I)/Au(III) catalysis has been achieved.
Garciyunnanimines A–C, novel cytotoxic polycyclic polyprenylated acylphloroglucinol imines from Garcinia yunnanensis
Novel cytotoxic PPAP imines from G. yunnanensis and the biomimetic synthesis of PPAP imines from corresponding PPAPs.
Palladium catalyzed C(sp3)–H acetoxylation of aliphatic primary amines to γ-amino alcohol derivatives
It still remains a major challenge to apply free primary amino groups as the directing group for aliphatic C–H functionalization.
Asymmetric SN2′-type C–H functionalization of arenes with propargylic alcohols
The first example of transition metal-catalyzed stereo-defined syn-β-OH elimination! A [Cp*RhCl2]2-catalyzed allenylation reaction of available arenes with propargylic alcohols afforded fully substituted allenes with excellent ees.
Concise asymmetric total synthesis of (−)-patchouli alcohol
An asymmetric total synthesis of (−)-patchouli alcohol was realized featuring an enantioselective organocatalytic [4 + 2] approach to the [2.2.2] bicyclic core.
The asymmetric synthesis of multisubstituted diquinanes via the domino reaction of electron-deficient enynes
A series of chiral multisubstituted diquinanes containing three continuous chiral centers are obtained in good yields with excellent enantioselectivities.
Iridium-catalyzed direct asymmetric reductive amination of aromatic ketones
Diphenylmethanamine offers excellent stereocontrol and easy deprotection to provide primary amines in the studied asymmetric reductive amination.
Merging photoredox catalysis with transition metal catalysis: site-selective C4 or C5-H phosphonation of 8-aminoquinoline amides
A simple and efficient protocol for the transition metal-catalyzed site-selective C–H phosphonation of 8-aminoquinoline at the C4 or C5 positions via a photoredox process was developed.
Silver-mediated fluorination of alkyl iodides with TMSCF3 as the fluorinating agent
The first example of a silver-mediated fluorination of alkyl iodides with the Ruppert–Prakash reagent (TMSCF3) as the fluorinating agent is reported.
Fe-Catalyzed insertion of fluoromethylcarbenes generated from sulfonium salts into X–H bonds (X = Si, C, P)
The Fe-catalyzed insertion of fluoromethylcarbenes including trifluoromethylcarbene and difluoromethylcarbene into X–H (X = Si, C and P) bonds is described.
Efficient trifluoromethylation via the cyclopropanation of allenes and subsequent C–C bond cleavage
Trifluoromethyl has been efficiently incorporated into organic skeletons via allene cyclization and C–C bond cleavage.
Synthesis of dibromo- and tetrabromo-bipyrrolines and their corresponding 2,6-diazasemibullvalene derivatives
Treatment of Δ1-dipyrrolines with NBS afforded α,α′-dibromo-Δ1-bipyrrolines and α,α,α′,α′-tetrabromo-Δ1-bipyrrolines, which were efficiently transformed into 2,6-diazasemibullvalene derivatives via reduction with lithium.
A benzothiadiazole-based fluorescent sensor for selective detection of oxalyl chloride and phosgene
A turn-on fluorescent sensor based on benzothiadiazole was constructed for simultaneous selective and visual detection of oxalyl chloride and phosgene.
Transition-metal-free dehydrogenation coupling of pyridinium through a self-promoted hydride transfer process
An intramolecular dehydrogenation coupling between phenol and pyridinium through a unique substrate self-promoted hydride transfer process has been developed.
Asymmetric synthesis of chromans via the Friedel–Crafts alkylation–hemiketalization catalysed by an N,N′-dioxide scandium(III) complex
The direct and sequential Friedel–Crafts alkylation/hemiketalization procedures for the synthesis of chiral chromans resulted in excellent yields, high enantioselectivities and high diastereoselectivities for a broad range of substrates.
Photoinduced difunctionalization of 2,3-dihydrofuran for the efficient synthesis of 2,3-disubstituted tetrahydrofurans
An efficient photoinduced multicomponent difunctionalization of 2,3-dihydrofuran has been developed for the synthesis of 2,3-disubstituted tetrahydrofurans under mild reaction conditions.
The influence of branched alkyl side chains in A–D–A oligothiophenes on the photovoltaic performance and morphology of solution-processed bulk-heterojunction solar cells
Besides providing sufficient solubility, branched alkyl chains also affect the film-forming and packing properties of organic semiconductors.
Synthesis of pyrazolo[5,1-a]isoquinolines through copper-catalyzed regioselective bicyclization of N-propargylic sulfonylhydrazones
An expeditious strategy for the synthesis of pyrazolo[5,1-a]isoquinolines through copper(II)-catalyzed regioselective bicyclization of N-propargylic sulfonylhydrazones has been developed.
Synthesis and conformational structure of hydrazo-bridged homo calixpyridinetriazines
Presented in this paper are the practical synthesis and conformational structure of hydrazo-bridged homo calixarenes.
Copper-catalyzed oxidative amidation of α,β-unsaturated ketones via selective C–H or C–C bond cleavage
The copper-catalyzed oxidative amidation of α,β-unsaturated ketones with N-fluorobenzenesulfonimide (NFSI) via a highly regioselective cleavage of C(CO)–C(vinyl) or C(vinyl)–H bonds of ketones has been achieved.
Squaramide-catalyzed domino Michael/aza-Henry [3 + 2] cycloaddition: asymmetric synthesis of functionalized 5-trifluoromethyl and 3-nitro substituted pyrrolidines
The diastereo- and enantioselective Michael/aza-Henry [3 + 2] cycloaddition reaction of trifluoromethyl-substituted iminomalonate and nitroalkenes has been developed employing 10 mol% of a quinine-squaramide catalyst.
Asymmetric synthesis of CF3- and indole-containing tetrahydro-β-carbolines via chiral spirocyclic phosphoric acid-catalyzed aza-Friedel–Crafts reaction
An enantioselective aza-Friedel–Crafts reaction of indoles with 1-trifluoromethyl-3,4-dihydro-β-carbolines has been developed to afford tetrahydro-β-carbolines with a CF3- and indole-containing quaternary stereocenter by using chiral phosphoric acid catalysis.
Radical cyclization of benzene-tethered 1,7-enynes with aryldiazonium tetrafluoroborates: a facile route to benzo[j]phenanthridines
A radical cyclization of benzene-tethered 1,7-enynes with aryldiazonium tetrafluoroborates in the presence of copper(II) acetate and DABCO˙(SO2)2 is developed, leading to diverse benzo[j]phenanthridines.
Direct copper-catalyzed oxidative trifluoromethylthiolation of aryl boronic acids with AgSCF3
A copper-catalyzed direct oxidative trifluoromethylthiolation of aryl boronic acids with AgSCF3 has been developed.
Copper-catalyzed highly selective approach to 2-boroallylic silanes from allenylsilanes
A highly selective copper-catalyzed borylcupration of 1,2-allenylsilanes affords 2-borylallylsilanes with many synthetically attractive functional groups by applying BIPHEP as the ligand has been developed.
Highly enantioselective nitro-Mannich reaction of ketimines under phase-transfer catalysis
A novel bifunctional phase-transfer catalyst 1i was found to be highly efficient for the nitro-Mannich reaction of unactivated ketone-derived imines with the introduction of the protecting group 6-methyl-2-pyridylsulfonyl to the ketimines. Density functional theory (DFT) calculations are also performed to give the possible transition-state model.
Enantioselective synthesis of naturally occurring isoquinoline alkaloids: (S)-(−)-trolline and (R)-(+)-oleracein E
The highly efficient asymmetric synthesis of a pair of enantiomers, (S)-(−)-trolline and (R)-(+)-oleracein E, has been achieved in five steps.
Iridium-catalyzed asymmetric hydrogenation of cyclic iminium salts
An iridium-catalyzed asymmetric hydrogenation of cyclic iminium salts has been developed, affording products with up to 96% ee.
A facile approach to ketones via Pd-catalyzed sequential carbonylation of olefins with formic acid
An effective palladium-catalyzed sequential carbonylation of olefins with formic acid is described.
Synthesis of 3-((arylsulfonyl)methyl)indolin-2-ones via insertion of sulfur dioxide using anilines as the aryl source
Facile assembly of 3-((arylsulfonyl)methyl)indolin-2-ones via insertion of sulfur dioxide starting from anilines, N-arylacrylamides and DABCO·(SO2)2 is realized.
A chiral ion-pair photoredox organocatalyst: enantioselective anti-Markovnikov hydroetherification of alkenols
A chiral ion-pair photoredox organocatalyst was reported to facilitate visible-light-meditated asymmetric anti-Markovnikov hydroetherification of alkenols with high reactivity and moderate enantioselectivity.
KBr/K2S2O8-mediated dibromohydration of N-(2-alkynylaryl)acetamide
A neighbouring acetamino group-participated regioselective dibromohydration of N-(2-alkynylaryl)acetamide is described here for the synthesis of N-(2-(2,2-dibromo-2-arylacetyl)aryl)acetamide.
(1S)-(−)-N-Trifluoromethylthio-2,10-camphorsultam and its derivatives: easily available, optically pure reagents for asymmetric trifluoromethylthiolation
Optically pure reagents that are able to deliver a trifluoromethylthio group with good to excellent enantioselectivities.
Thiolate–palladium(IV) or sulfonium–palladate(0)? A theoretical study on the mechanism of palladium-catalyzed C–S bond formation reactions
Thiolate–palladium(IV) intermediates are generated through oxidative addition in our suggested mechanisms, and are the key intermediates in these catalytic cycles.
Phosphine-mediated domino reactions of phthalimidomalonates with allenoates or but-2-ynoate: facile entry into highly functionalized pyrroloisoindolinone derivatives
A phosphine-mediated γ-umpolung/Wittig/γ-umpolung reaction between phthalimidomalonates and allenoates/but-2-ynoate furnishes highly functionalized pyrroloisoindolinone derivatives in synthetically useful yields.
The impact of interplay between electronic and steric effects on the synthesis and the linear and non-linear optical properties of diketopyrrolopyrrole bearing benzofuran moieties
Benzofuran has been proven to be the versatile substituent for tuning the optics of diketopyrrolopyrroles.
The first azacorannulene with a nitrogen on the rim, has been synthesized in seven steps from 4-bromoisoquinoline.
From tetrabenzoheptafulvalene to sp2 carbon nano-rings
A new kind of sp2 carbon nano-rings containing a heptagon and an octagon was synthesized by taking advantage of the “C” shape of syn-tetrabenzoheptafulvalene.
Silver-catalyzed radical carbofluorination of unactivated alkenes with acetic acid in aqueous solution
The AgNO3-catalyzed carbofluorination of unactivated alkenes with acetic acid provides an efficient and general route to γ-fluorinated carboxylic acids.
Iridium catalysts with modular axial-unfixed biphenyl phosphine–oxazoline ligands: asymmetric hydrogenation of α,β-unsaturated carboxylic acids
Axial-unfixed biphenyl phosphine–oxazoline ligands were successfully applied to Ir-catalyzed asymmetric hydrogenation of α,β-unsaturated carboxylic acids.
One-pot synthesis of fluorescent 2,4-dialkenylindoles by rhodium-catalyzed dual C–H functionalization
A one-pot synthesis of fluorescent 2,4-dialkenylindoles by rhodium-catalyzed dual C–H bond alkenylation of indoles.
About this collection
Read some of the best research published from Organic Chemistry Frontiers in 2017. These articles are recommended by reviewers as being of significant novelty and interest.