Alireza Ariafard

Alireza Ariafard
University of Tasmania · School of Chemistry

PhD

About

162
Publications
8,492
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2,788
Citations
Citations since 2016
83 Research Items
1722 Citations
2016201720182019202020212022050100150200250300350
2016201720182019202020212022050100150200250300350
2016201720182019202020212022050100150200250300350
2016201720182019202020212022050100150200250300350

Publications

Publications (162)
Article
Full-text available
The 2-iodoxybenzoic acid (IBX)-controlled oxidative dearomatization of pyrroles occurs very slowly (or not all) in many organic solvents, including DMSO in which IBX is soluble. Interestingly, although IBX is only partially soluble in acetic acid, this solvent mediates the pyrrole oxidative dearomatization. With the aid of density functional theory...
Article
Density functional theory (DFT) has been used to investigate the mechanism of the experimentally efficient hydroalkylation of styrene with acetylacetone in the presence of a bismuth catalyst. It is shown that the mechanism is fundamentally different to that of the analogous gold-catalysed reaction, even though it leads to the same product. Whereas...
Article
The synthesis of benzofurans by the reaction of the palladium(II) complex Pd{1-C6H4-2-OCH(CO2Et)-C,C}(bipy) (bipy = 2,2'-bipyridine) with hypervalent iodine(III) reagents [Ph(CHCHR)I]+ has been examined by Density Functional Theory. Results highlight the role of oxidative alkenylation to form PdIV intermediates and the role of initial adduct forma...
Article
An efficient chiral gold(I) complex-catalyzed synthetic method that enables the cycloisomerization/regio- and enantioselective nitroso-Diels-Alder (NDA) reaction of 1,6-diyne esters with nitrosobenzenes is described. The sequential ring formation protocol offers access to a wide variety of 3,5,6,8a-tetrahydro-1H-benzo[c][1,2]oxazines as a single re...
Article
Full-text available
An efficient and mild reaction protocol for the decarbonylation of isocyanates has been developed using catalytic amounts of Lewis acidic boranes. The electronic nature (electron withdrawing, electronically neutral, and electron donating) and the position of the substituents ( ortho / meta / para ) bound to isocyanate controls the chain length and...
Article
Thermally induced cycloisomerization reactions of 1,6‐allenynes gives α‐methylene‐γ‐lactams via intramolecular Alder‐ene reactions. The mechanism is supported by computational and deuterium labelling studies. This thermal, non‐radical method enables the discovery of a hitherto unknown route that proceeds via a divergent mechanism distinct from the...
Article
Full-text available
Diazo compounds have been largely used for carbene transfer reactions in a variety of functionalization reactions. Recently, tris(pentafluorophenyl)borane [B(C 6 F 5 ) 3 ] has been shown to be an efficient metal-free catalyst for carbene transfer reactions. Herein, we report a Density Functional Theory (DFT) study on the generation of carbene speci...
Article
Decomposition of donor‐acceptor diazo compounds leads to the formation of reactive carbene intermediates. These can undergo a wide variety of carbene transfer reactions to yield synthetically useful products. Herein, we report a highly selective borane catalyzed cyclization reaction from the combination of two different diazo compounds to afford N‐...
Article
Density functional theory studies of bridge‐splitting of [PtIIR2(SEt2)]2 (R = 4‐tolyl) by bromoarenes containing nitrogen donor groups, subsequent intramolecular coordination assisted oxidative addition, and reductive elimination elucidate the mechanism for formation of mer‐PtII(N,C,N)Br pincers via PtIV, where the pincers have applications in fund...
Article
Full-text available
In recent years, metal-free organic synthesis using triarylboranes as catalysts has become a prevalent research area. Herein we report a comprehensive computational and experimental study for the synthesis of highly selective N-substituted pyrazoles through the generation of carbenium species from the reaction between aryl esters and vinyl diazoace...
Article
In recent years, metal-free organic synthesis using triarylboranes as catalysts has become a prevalent research area. Herein we report a comprehensive computational and experimental study for the synthesis of highly selective N-substituted pyrazoles through the generation of carbenium species from the reaction between aryl esters and vinyl diazoace...
Article
We thoroughly investigated mechanistic features of dichlorination of diazoacetates using PhICl2 catalysed by pyridine. We found that the pyridine serves as a catalyst for decomposition of PhICl2 to PhI and...
Article
Density functional theory computation indicates that bridge‐splitting of [Pt II R 2 (μ‐SEt 2 )] 2 proceeds via partial dissociation to form R 2 Pt a (μ‐SEt 2 )Pt b R 2 (SEt 2 ), followed by coordination of N‐donor bromoarenes (L‐Br) at Pt a leading to release of Pt b R 2 (SEt 2 ), which reacts with a second molecule of L‐Br, providing two molecules...
Preprint
Full-text available
Hypervalent iodine(V) (HVI) compounds are highly efficient reagents for the double oxidative dearomatization of electron-rich phenols to o-quinones. We recently reported that an underexplored class of iodine(V) reagents possessing bidentate bipyridine ligands, termed Bi(N)-HVIs, could efficiently dearomatize electron-poor phenols for the first time...
Preprint
Hypervalent iodine(V) (HVI) compounds are highly efficient reagents for the double oxidative dearomatization of electron-rich phenols to o-quinones. We recently reported that an underexplored class of iodine(V) reagents possessing bidentate bipyridine ligands, termed Bi(N)-HVIs, could efficiently dearomatize electron-poor phenols for the first time...
Article
Full-text available
Strategies that enable intermolecular site-selective C–H bond functionalisation of organic molecules provide one of the cornerstones of modern chemical synthesis. In chloroalkane synthesis, such methods for intermolecular site-selective aliphatic C–H bond chlorination have, however, remained conspicuously rare. Here, we present a copper(I)-catalyse...
Article
Hypervalent iodine(V) reagents are a powerful class of organic oxidants. While the use of I(V) compounds Dess-Martin periodinane and IBX is widespread, this reagent class has long been plagued by issues of solubility and stability. Extensive effort has been made for derivatizing these scaffolds to modulate reactivity and physical properties but con...
Article
Full-text available
Although Pd(OAc)2-catalysed alkoxylation of the C(sp3)-H bonds mediated by hypervalent iodine(III) reagents (ArIX2) has been developed by several prominent researchers, there is no clear mechanism yet for such crucial transformations....
Article
Full-text available
The donor–acceptor ability of frustrated Lewis pairs (FLPs) has led to widespread applications in organic synthesis. Single electron transfer from a donor Lewis base to an acceptor Lewis acid can generate a frustrated radical pair (FRP) depending on the substrate and energy required (thermal or photochemical) to promote an FLP into an FRP system. H...
Article
Full-text available
Iodosobenzene (PhIO) is known to be a potent oxidant for alcohols in the presence of catalytic bromide in water. In order to understand this important and practical oxidation process, we have conducted density functional theory studies to shed light on the reaction mechanism. The key finding of this study is that PhIO is not the reactive oxidant it...
Article
We report a N-heterocyclic carbene copper(I) complex-catalysed formal cycloaddition between readily available propargylic alcohols and carbon dioxide at room temperature. By using the combination of a sterically demanding BPDPrCuCl complex (BPDPr = 1,3-bis(2,6-diisopropylphenyl)-1,3-diazonine-2-ylidene) and CsF, as catalytic system, primary proparg...
Article
We have identified and extensively investigated the photochemical activation and reaction of a hydroxyquinone-derived phenyliodonium ylide in the presence of visible light using experiment and theory. These studies revealed that in its photoexcited state this iodonium is capable of facilitating a range of single-electron transfer (SET) processes, i...
Article
Full-text available
A simple gold‐catalyzed annulation of 1,8‐dialkynylnaphthalenes utilizing a cationic gold catalyst was developed. Such a peri‐position of two alkynyl substituents has not been studied in gold catalysis before. Dependent on the substrate, the reactions either follow a mechanism involving vinyl cation intermediates or involve a dual gold catalysis me...
Article
Density functional theory (DFT) was utilized to understand how bismuth(III) salts (BiX3) achieve greatest activation of organic Lewis bases in a catalytic reaction. It is reported in the literature that the BiX3 reactivity originates from its low lying Bi−X σ* orbital. In contrast to this belief, we will show here that for BiX3 to effectively serve...
Article
A combination of iodosobenzene (PhIO) and molecular iodine (I2) is well-documented to produce a key species capable of conducting various organic reactions through radical mechanisms. This key species is identified here by density functional theory (DFT) calculations to be the hypoiodite radical (IO). The calculations show that two equivalents of I...
Article
Full-text available
Efficient methods for the synthesis of fused-aromatic rings is a critical endeavour in the creation of new pharmaceuticals and materials. A direct method for preparing these systems is the tetradehydro-Diels–Alder reaction, however this is limited by the need for harsh reaction conditions. A potential, but underdeveloped, route to these systems is...
Article
The oxidant diphenyldiselenide reacts with MIIMe2(bipy) (bipy = 2,2'-bipyridine) to form a pre-equilibrium involving weak adducts, from which [MMe2(bipy)]2·Ph2Se2 undergoes rate-limiting dissociation of phenylselenide preceded by the oxidative addition step to obtain [Me2(bipy)M-MMe2(bipy)(SePh)]+. Coordination of PhSe- gives the neutral MIII-MIII...
Article
Full-text available
The ability of halogenated triarylboranes to accept a lone pair of electrons from donor substrates renders them excellent Lewis acids which can be exploited as a powerful tool in organic synthesis. Tris(pentafluorophenyl)borane has successfully demonstrated its ability to act as a metal-free catalyst for an ever-increasing range of organic transfor...
Article
Density Functional Theory studies of square‐planar Pt II pincer structures, (4‐Z‐NCN)PtCl ([4‐Z‐NCN] ‐ = [4‐Z‐2,6‐(Me 2 NCH 2 ) 2 C 6 H 2 ‐ N,C,N ] ‐ , Z = H, NO 2 , CF 3 , CO 2 H, CHO, Cl, Br, I, F, SMe, SiMe 3 , t Bu, OH, NH 2 , NMe 2 ), enable characterisation of mesomerism for the pincer‐Pt interaction. Relationships between Hammett s p substit...
Article
Full-text available
Lewis acidic boranes have been shown to be effective metal-free catalysts for highly selective reactions of donor-acceptor diazo compounds to a range of substrates. The reactions of α-aryl α-diazoesters with nitrogen heterocycles indole or pyrrole selectively generate C3 and C2 C–H insertion products, respectively, in good to excellent yields even...
Article
Full-text available
Aus 2 wird 1: Lewis‐saure Borane werden in den metallfreien Alkenylierungsreaktionen von Arylestern mit α‐Diazoestern eingesetzt, um hochfunktionalisierte Alken‐, Enin‐ und Dienprodukte in guten bis ausgezeichneten Ausbeuten zu erhalten. DFT‐Studien klären den Mechanismus der Reaktion auf. Abstract Wir berichten hier von einer einfachen und milden...
Article
Full-text available
Herein we report a facile, mild reaction protocol to form carbon‐carbon bonds in the absence of transition metal catalysts. We demonstrate the metal‐free alkenylation reactions of aryl esters with α‐diazoesters to give highly functionalized enyne products. Catalytic amounts of tris(pentafluorophenyl)borane (10–20 mol%) are employed to afford the C=...
Article
Density functional theory (DFT) at the SMD/M06‐2X/def2‐TZVP//SMD/M06‐2X/SDD,6‐31G(d) level was performed to interrogate the mechanistic details of two oxidative fluorination reactions mediated by hypervalent iodosoarenes (ArIO) in the presence of Lewis acid BF3: (i) formation of a 3‐fluoropyrrolidine from a homoallylic amine and (ii) formation of a...
Article
Full-text available
Density functional theory was utilized to investigate plausible mechanisms for amine and alcohol oxidation by an iodine(V) hypervalent reagent (IBX). In this contribution, we found that amine and alcohol oxidation both proceed by similar mechanisms. The reactions initiate from ligand exchange to give four coordinate intermediates followed by a redo...
Article
A synthetic method to prepare cycloalkyl‐ and (hetero)aryl‐fused bicyclo[3.3.1]nonane derivatives from gold(I)‐catalyzed cyclopropanation/[5+3] cycloaddition of 1,4,9‐ and 1,4,10‐allenenynes is described. The suggested double cycloisomerization mechanism delineates the first example of a stepwise [5+3] cycloaddition pathway in gold catalysis, a mod...
Article
This Article demonstrates a mild oxidatively induced C(sp3)-H activation at a high-valent Ni center. In contrast with most C(sp3)-H activation reactions at NiII, the transformation proceeds at room temperature and generates an isolable NiIV σ-alkyl complex. Density functional theory studies show two plausible mechanisms for this C-H activation proc...
Article
We report a switchable synthesis of acylindoles and quinoline derivatives via gold‐catalyzed annulations of anthranils and ynamides. With an N,O‐ligand on a gold(III) catalyst α‐imino gold carbenes, in situ generated from anthranils, could undergo electrophilic attack to the aryl π‐bond followed by unexpected and highly selective 1,4‐ or 1,3‐acyl m...
Article
Full-text available
We report a switchable synthesis of acylindoles and quinoline derivatives via gold‐catalyzed annulations of anthranils and ynamides. With an N,O‐ligand on a gold(III) catalyst α‐imino gold carbenes, in situ generated from anthranils, could undergo electrophilic attack to the aryl π‐bond followed by unexpected and highly selective 1,4‐ or 1,3‐acyl m...
Article
The treatment of pyridine- and pyrazole-ligated NiII σ-aryl complexes with Selectfluor results in C(sp2)-F bond formation under mild conditions. With appropriate design of supporting ligands, diamagnetic NiIV σ-aryl fluoride intermediates can be detected spectroscopically and/or isolated during these transformations. These studies demonstrate for t...
Article
This Article describes the development of a stable NiIV complex that mediates C(sp2)-H trifluoromethylation reactions. This reactivity is first demonstrated stoichiometrically and then successfully translated to a NiIV-catalyzed C-H trifluoromethylation of electron-rich arene and heteroarene substrates. Both experimental and computational mechanist...
Article
Full-text available
Precise control of the selectivity in organic synthesis is important to access desired molecule. We demonstrated a regiospecific annulation of asymmetric 1,2‐di(arylethynyl)benzene derivatives for a geometry controlled synthesis of a linear bispentalene which is one of the promising structures for material science. Gold‐catalyzed annulation of asym...
Article
Full-text available
In contrast to early transition metal complexes of d0 electron configuration, their main group metal analogues are usually poor catalysts for ethylene polymerisation due to their diminished tendency to insert ethylene into an M-R bond. Interestingly, we found that ring strain in the transition structure of the insertion reaction is most likely resp...
Article
Density functional theory (DFT) was used to investigate PR3AuOTf-catalyzed hydrofunctionalisation of nonactivated alkenes using acetic acid and phenol where OTf = triflate (CF3SO3‒). The gold(I) complex itself is found to be unlikely to operate as the π-activator due to its relatively low electrophilicity. Instead, the concurrent coordination of tw...
Article
Gas-phase ion trap mass spectrometry experiments and density functional theory calculations have been used to examine the routes to the formation of the 1,8-naphthyridine (napy) ligated geminally dimetallated phenyl complexes [(napy)Cu2(Ph)]+, [(napy)Ag2(Ph)]+ and [(napy)CuAg(Ph)]+ via extrusion of CO2 or SO2 under collision-induced dissociation co...
Article
We have used density functional theory to explore the copper(I)-catalyzed reaction between a mesyl azide and a terminal alkyne that leads to a ketenimine whose interaction with nucleophilic water produces an amide. It is well reported in the literature that a cuprated triazole intermediate is formed during the course of such a catalytic cycle. In t...
Article
Doppelte Gold‐Aktivierung ist ein wichtiges Motiv in der homogene Katalyse. In ihrer Zuschrift (DOI: 10.1002/ange.201810794) zeigen S. Pyne und C. J. T. Hyland et al., dass E‐Endiine unter dualer Goldkatalyse eine Cycloaromatisierung zu Isoindolinonen eingehen. Elektronisch differenzierte Dreifachbindung führen zur Bildung eines bestimmten Propiol‐...
Article
Dual gold‐activation is an important catalytic mode in homogenous catalysis. In their Communication (DOI: 10.1002/anie.201810794), S. G. Pyne and C. J. T. Hyland et al. report that (E)‐enediynes undergo a dual gold‐catalyzed cycloaromatization towards isoindolinones. They use electronic‐differentiation of triple bonds to direct the formation of a p...
Article
A palladium-mediated one-pot synthesis of amidines from aromatic carboxylic acids and carbodiimides (RNCNR) is reported as an isoelectronic adaption of CO2ExIn (ExIn = Extrusion-Insertion) reactions developed for the synthesis of thioamides from carboxylic acids and isothiocyanates (RNCS). Multistage mass spectrometry (MSⁿ) experiments for model sy...
Article
A synthesis of unconjugated (E)‐enediynes from allenyl amino alcohols is reported and their gold‐catalyzed cascade cycloaromatization to a broad range of enantioenriched substituted isoindolinones has been developed. Experimental and computational studies support the reaction proceeding via a dual‐gold σ,π‐activation mode, involving a key gold‐viny...
Article
The Nazarov cyclisation is an important and reliable reaction for the synthesis of cyclopentenones. Density functional theory (DFT) has been utilised to study the mechanism of Nazarov cyclisations initiated by oxidation of pentadienyl ethers by a benzoquinone derivative (DDQ), as recently reported by West et. al (Angew. Chem. Int. Ed., 2017, 56, 63...
Article
A synthesis of unconjugated (E)‐enediynes from allenyl amino alcohols is reported and their gold‐catalyzed cascade cycloaromatization to a broad range of enantioenriched substituted isoindolinones has been developed. Experimental and computational studies support the reaction proceeding via a dual‐gold σ,π‐activation mode, involving a key gold‐viny...
Article
A PtIV prodrug needs to be reduced to PtII by a biomolecule in order to show efficacy. Among biomolecules, those containing an L-Cys residue have the highest potential to be...
Article
A DFT study of alkyl halide exchange from Pd(IV) to Pd(II) centers supports proposals for an SN2 process in which nucleophilic Pd(II) square-planar complexes attack the axial alkyl group in electrophilic square-pyramidal Pd(IV) centers, leading to transfer of R⁺ from Pd(IV) to Pd(II) involving a transition structure of the form [R2(bpy)··R··PdR2 (b...
Article
Full-text available
Density functional theory (DFT) was utilized to explore the reduction of gold(III) complexes by the amino acid glycine (Gly). Interestingly, we found that when the nitrogen atom of Gly coordinates to the gold(III) center, its Cα‐hydrogen atom becomes so acidic that it can be easily deprotonated by a mild base like water. The deprotonation converts...
Article
A combination of gas-phase ion trap mass spectrometry experiments and density functional theory (DFT) calculations have been used to examine the role of substituents on the decarboxylation of 25 different coordinated aromatic carboxylates in binuclear complexes, [(napy)Cu2(O2CC6H4X)]⁺, where napy is the ligand 1,8-naphthyridine (molecular formula,...
Article
The mechanism for the [PtIICl4]2--catalysed reaction of Ph2IIII(TFA) (TFA = trifluoroacetate) with naphthalene (NapH) to give β-phenylation over α-phenylation of naphthalene has been examined by computational methods. In support of the mechanism proposed by Sanford based on experimental evidence, reaction commences by oxidative phenyl transfer from...