Anthony J. Arduengo

Anthony J. Arduengo
Georgia Institute of Technology | GT · School of Chemistry and Biochemistry

Ph.D. 1976 Georgia Institue of Technology

About

218
Publications
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Introduction
Anthony J. Arduengo is Professor of the Practice at Georgia Tech. Current research activities include compounds with unusual valency, new functional group chemistry, sustainable chemistry from wood (Xylochemstry), and development of efficient syntheses for active pharmaceutical intermediate. Through the effort in Xylochemstry an active scholar exchange, and study & research abroad program is sponsored jointly between the University of Alabama and the Johannes Gutenberg Universität-Mainz.
Additional affiliations
June 2020 - present
Georgia Institute of Technology
Position
  • Professor
January 2018 - present
University of Alabama
Position
  • Professor Emeritus
October 1999 - December 2017
University of Alabama
Position
  • Professor
Description
  • Teaching, Research

Publications

Publications (218)
Article
This article surveys a range of important platform and high value chemicals that may be considered primary and secondary 'xylochemicals'. A summary of identified xylochemical substances and their natural sources is provided in tabular form. In detail, this review is meant to provide useful assistance for the consideration of potential synthetic str...
Article
The structural and energetic reactivities of various carbenes are evaluated against a standard electrophile (proton) and a standard nucleophile (fluoride). The proton and fluoride affinities of the carbenes studied provide an increased understanding of reactivity modes and mechanisms. General classification of carbenic reactivity as singlet nucleop...
Article
Herein, we report further improvements to the synthesis of tenofovir 1, the precursor to tenofovir disoproxil fumarate (TDF) and tenofovir alafenamide fumarate (TAF). Starting from acyclic precursor diaminomalononitrile 12, a four-step protocol to tenofovir 1 will allow for vertical integration for more manufacturers. The key transformation is a co...
Preprint
p>Abstract: Herein, we report further improvements to the synthesis of tenofovir 1 , the precursor to tenofovir disoproxil fumarate and tenofovir alafenamide fumarate. Starting from acyclic precursor diaminomalononitrile 12 , a four-step protocol to tenofovir 1 will allow for vertical integration for more manufacturers. The key transformation is a...
Article
N-Substituted amidinoimidazoles and amidinopyrroles were synthesized by the reaction of 2-cyanoimidazole and 2-cyanopyrrole with the corresponding ammonium salts in the presence of AlMe3 in toluene under reflux conditions. With the aim to investigate the transformation of the N-substituted amidino group to isonitrilium ion, N-mesitylamidinoimidazol...
Article
The solid-state structures of the Burgess reagent, and its analogous ethyl ester reveal structures indicative of triethylamine solvated sulfonyl imides rather than the more commonly depicted triethylammonium sulfonyl amidate. The existence of a reversibly formed hydrate of Burgess reagent is not supported by present studies, but rather a hydrosylat...
Article
There is an urgent demand for 5‐fluorocytosine (5‐FC) due to its activity against HIV‐induced fungal infections as well as its use as a key intermediate in the synthesis of the clinically highly important anti‐HIV drug emtricitabine (FTC). We report a simple, low‐cost five steps synthesis of 5‐FC starting from chloroacetamide. Overall yields up to...
Conference Paper
Full-text available
This presentation traces a thread of chemical evolution involving nitrile oxides / nitroso carbenes from the 17th Century through to the 21st Century. Recent application of these curious materials as active pharmaceutical ingredients (APIs) in service to the global Medicines for All Initiative sponsored by the Bill & Melinda Gates Foundation will b...
Article
The hydrogenation energies and singlet-triplet (S-T) splittings at the G3MP2 level of theory have been calculated for a wide range of carbenes. The carbene, :CXY with different substituents (X, Y = H, CN, NC, F, Cl, OH, OCH3, CH3, CF3, SiH3, SiMe3, phenyl, CH=O, PH2, and NH2) at the carbenic carbon center, immidazole-based carbenes, Bertrand's carb...
Conference Paper
Full-text available
The structures and chemistry of imidazolium salts and imidazol-2-ylidenes bearing strained substituents is discussed.
Article
Against the backdrop of modern sustainable chemistry and valorization of biomass for chemical raw materials, the syntheses of indigo dyes and polyamides as representatives of two classes of everyday chemical products based on xylochemicals are described. Wood-derived starting materials were transformed into functional materials using the principles...
Conference Paper
Full-text available
In 2004 Clyburne et al. reported the oxidation of imidazol-2-ylidenes with the one-electron oxidants ferrocenium ion and tetracyanoethylene (TCNE).[1] However, neither the ferrocenium ion nor TCNE are strong enough oxidants to abstract an electron from the imidazol-2-ylidenes studied. The chemistry of imidazol-2-ylidenes with TCNE had been previous...
Article
A concise and efficient synthesis of (3R,3aS,6aR)-hexahydrofuro[2,3-b]furan-3-ol, a key building block for several clinical and experimental HIV protease inhibitors including the highly important drug Darunavir, was achieved via a one-pot procedure using furan and Cbz-protected glycol aldehyde as starting materials. A [2+2]-photocycloaddition betwe...
Article
1,3-Bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene forms stable 1:1 adducts with tetrafluoroethylene (2), hexafluorocyclobutene (3) and octafluorocyclopentene (4). Adduct 2 shows properties typical for non-polarized olefins, as indicated by NMR spectroscopy and X-ray crystallography. By contrast, adducts 3 and 4 are best described as ylides with a...
Article
Full-text available
Xylochemistry - the use of wood as a source of raw materials for chemical synthesis - provides a climate-neutral alternative to the conventional use of fossil carbon sources such as natural gas or oil. Illustratively, we reported the utilization of wood constituents as the sole carbon source for the production of complex chemical compounds and thus...
Article
The synthesis of M(CO) 5 complexes bearing 4-phosphonamide and 4,5-bis(phosphonamide)-imidazol-2-ylidene ligands (NHC P ¼ phosphonamide-based N-heterocyclic carbene) is reported. Deprotonation of respective imidazolium hydro-gensulfate salts with potassium tert-butoxide (KO t Bu) in the presence of [M(CO) 5 (CH 3 CN)] afforded complexes with the fo...
Article
Thumbnail image of graphical abstract “Carving” molecules out of wood. The synthesis of chemical materials from sustainable resources in an environmentally responsible way is an important grand challenge for a modern chemical infrastructure. In their Communication (DOI: 10.1002/anie.201508500), T. Opatz, A.J. Arduengo, et al. tackle the first of f...
Article
The first total synthesis of the dimeric berberine alkaloid ilicifoline (ilicifoline B) is reported. Its carbon skeleton is constructed from ferulic acid, veratrole, and methanol. The synthesis reported herein employs starting materials solely derived from wood. The natural product is thus constructed entirely from renewable resources. The same str...
Article
Das Schnitzen” von Molekülen aus Holz. Die umweltfreundliche Synthese chemischer Verbindungen aus nachhaltigen Ressourcen ist eine der großen Herausforderungen an eine moderne chemische Infrastruktur. In ihrer Zuschrift (DOI: 10.1002/ange.201508500) nehmen T. Opatz, A. J. Arduengo et al. den ersten von insgesamt vier Aspekten der Xylochemie in Angr...
Conference Paper
Full-text available
Reactions of extremely electron poor olefins with highly electron-rich imidazol-2-ylidenes will be discussed. A variety of zwitterionic (inner salt) products are obtained that contain imidazolium ions bound to delocalized carbanionic fragments.
Article
The interaction of electron rich imidazol-2-ylidenes with electron poor cyanocarbons is reported. Contrary to previous reports of electron transfer products from imidazol-2-ylidenes and tetracyanoethylene, a number of ring forming cyanocarbon ring structures are isolated and characterized. Cyanation of the imidazole ring was explored by the additio...
Article
Full-text available
Selective synthesis of 4-phosphanylated imidazole-2-thiones 2d, 3a,b(b′),c(c′),d were achieved using a backbone lithiation and phosphanylation reaction protocol. The 4-phosphanylated-imidazole-2-thiones 3b(b′),c(c′) were subjected to a oxidation/phosphanylation/oxidation reaction sequence to access C4/5-bis(phosphanoyl)-substituted imidazole-2-thio...
Article
Coupled cluster theory [CCSD(T)] with the aug-cc-pVDZ/aug-cc-pVDZ-PP basis sets is used to predict the thermodynamic properties of models of the Grubbs catalyst, H2ImM(PH3)(CRR′) and H2ImM(C2H4)(CRR′) for M = Fe, Ru, and Os and CRR′ = CH2, CHF, and CF2. The PH3 and C2H4, imidazolinium carbene (H2Im), and CRR′ bond dissociation energies (BDEs) are r...
Article
Mild oxidation of zwitterionic azolium alkoxides (I) and (III) under anhydrous conditions leads to new stable spirocyclic ketals (II) and (IV).
Article
A crystallization method for 5-amidinium tetrazolide (1) was developed. Crystals of the pure zwitterion 1 enabled the unambiguous assignment of the structure as an inner-salt rather than the amidine tetrazole postulated previously. The solid-state structure of 1 consists of two sets of hydrogen bonds that form a tightly networked two-dimensional sh...
Article
Recent advances in the chemistry of heteroatom substituted carbenes, carbenium ions, carbanions, and carbon radicals, with emphasis on compounds that bear two heteroatoms are summarized. Herein a conceptual organization around chemical (synthetic) relationships among carbenes, carbenium ions, carbanions, and radicals is followed. Protonation/deprot...
Article
Full-text available
Neutral group 6B (Cr, Mo, W) pentacarbonyl complexes M(CO)5-L possessing various P-ligands such as phosphines, phosphaalkenes, and phospha-quinomethanes can form radical cations and anions under redox conditions. There is significant interest in whether the radical site is localized on the metal or on a "non-innocent" ligand. Density functional the...
Article
A Twist of Fate: Under oxidative conditions with iodosobenzene, a previously reported zwitterion meets a twisted fate. Oxidative cyclization of a series of imidazolium fluoroalkoxides provides access to a new class of fused imidazolone ketals.
Article
Stabile Harnstoffketale sind wegen ihrer Instabilität und Reaktivität nicht zugänglich. A. J. Arduengo III, J. W. Runyon et al. beschreiben nun in ihrer Zuschrift auf S. 11071 ff. die Oxidation einer Serie von Imidazoliumalkoxiden zu isolierbaren Imidazolon‐Spiroketalen. Die Spiralform dieses neuartigen anellierten Ringsystems erinnert an die Wende...
Article
Stable urea ketals have remained elusive because of their inherent instability and reactivity. In their Communication on page 10871 ff., A. J. Arduengo III, J. W. Runyon et al. describe the oxidation of a series of imidazolium alkoxides to produce isolable imidazolone spiroketals. The spiral nature of this novel fused‐ring system is reminiscent of...
Article
Complexes of unsymmetrically substituted N-heterocyclic carbenes with NMR-active metals (Ag, Hg, Pt) with or without a C-13-label in the 2-position were synthesized by aldimine cross coupling and analyzed with respect to the scalar couplings between the metal center or C2 and the other ring atoms.
Article
A synthetic route to C(4/5)-bis(phosphinoyl)imidazole-2-thiones () (d: R(1) = (n)Bu, R(2) = Me; e: R(1) = n-dodecyl, R(2) = Me) and C(4/5)-bis(thio/selenophosphinoyl)imidazole-2-thiones (), () and (a: R(1) = R(2) = Me; b: R(1) = R(2) = Ph, c: R(1) = (i)Pr, R(2) = Me) is presented that employs initial C(5) lithiation of mono-phosphinoyl/thiophosphin...
Conference Paper
Full-text available
An unusual ring-opening reaction of amidinium tetrazolide and thionyl chloride examined.
Conference Paper
Full-text available
New chelating singlet carbene structure are discussed along with structures leading to transient triplet carbenes.
Article
Gripping ligands: A series of fluoroalkoxy-functionalized imidazol-2-ylidene ligands were synthesized by the alkylation of a range of commercially available azoles with hexafluoroisobutylene oxide. The deprotonation of these species with a strong base cleanly generated the free carbenes, which acted as tridentate chelating ligands.
Article
Novel bis(imidazole-2-thion-4-yl)- phosphanes (2a–d) were synthesized via lithiation of the precursor imidazole-2-thiones followed by the phosphanylation reaction. Oxidation of bis(imidazole-2-thion-4-yl)phosphane 2b–d with elemental sulfur and selenium led selectively and in good yields to the P-thio (3b–d) and P-seleno (4c) derivatives of bis(imi...
Article
The thermodynamic properties of the potential hydrogen storage compounds, the borane adducts of pyrrole, pyrazole, imidazole, triazole, and tetrazole, were calculated at the G3MP2 level by using an isodesmic approach including experimental and accurate (CCSD(T)/CBS) values for the other components of the reaction. The heats of formation, bond disso...
Article
1-Alkyl-3-methyl-4-diphenylphosphoryl-imidazolium hydrogensulfate (4a,b) (a: R(1) = R(2) = Me; b: R(1) = (i)Pr, R(2) = Me) and 1-alkyl-3-methyl-4,5-bis(diphenylphosphoryl)imidazolium hydrogensulfate (6a,c) (c: R(1) = (n)Bu, R(2) = Me) were obtained selectively and in good yields by oxidative desulfurization of 1-alkyl-3-methyl-4-diphenylphosphino-i...
Article
Selective formation of 4-phosphanylated 1,2-dialkyl imidazole-2-thiones 3a-f has been obtained via a lithiation followed by phosphanylation reaction. The reactivity of 3a-f was examined towards oxidation and complexation reactions. All products were unambiguously characterized by elemental analyses, spectroscopic and spectrometric methods including...
Article
The formation of phosphinidenoid complex salts having weakly coordinating cations (WCCs) is reported via treatment of P-functional phosphane complexes with N,N’-di-tert-butyl imidazol-2-ylidene or a P4-t-Bu phosphazene base. The thermal stability of phosphinidenoid complex salts is dependent upon the P–X substituents and the nature of the WCC. The...
Article
The synthetic consequences of different basicities, nucleophilicities, and sterics of N-heterocyclic carbenes have been studied in reactions of imidazolin-2-ylidenes with organic halides. Highly nucleophilic and less basic carbenes cleanly gave alkylideneimidazolines, the deoxy analogues of Breslow-type intermediates. More basic NHCs engaged in unw...
Article
Carbenes fall in the area of compounds with unusual valency, which contain a divalent carbon. The typically high reactivity of carbenes and lack of suitable spectroscopy methods or laboratory techniques to handle these apparently transient species led to a widespread view that carbenes were too reactive to be isolated as stable entities. The versat...
Article
Full-text available
A series of Lewis acid–base pairs containing sterically demanding carbenes were investigated for hydrogen activation that could potentially be reversible for use in hydrogen storage applications. When electron-rich boranes are employed as electrophiles, the imidazolium cation is reduced to a 2H-imidazoline (aminal). The aminals were synthesized ind...
Article
Heats of formation, adiabatic and diabatic bond dissociation energies (BDEs) of the model Schrock-type metal complexes M(NH)(CRR′)(OH)2 (M = Cr, Mo, W; CRR′ = CH2, CHF, CF2) and MO2(OH)2 compounds, and Brønsted acidities and fluoride affinities for the M(NH)(CH2)(OH)2 transition metal complexes are predicted using high level CCSD(T) calculations. T...
Article
1-tert-Butyl-3-methyl-2,4-bis(2,4,6-tri-tert-butylphenyl)-1,3-diphosphacyclobutane-2,4-diyl reacts with hydride followed by proton quench to give a 2,4-diphospha-1,3-cyclobutadiene with diylidic structure.
Article
Intensive 1H-, 13C-, and 31P-NMR studies of 1-tert-butyl-3-methyl-2,4-bis(2,4,6-tri-tert-butylphenyl)-1,3-diphosphacyclobutane-2,4-diyl were perfomed to reveal several unusual coupling constants.
Article
Full-text available
Detailed 1H-, 13C-, and 31P NMR studies of 1-t-butyl-3-methyl-2,4-bis(2,4,6-tri-t-butylphenyl)-1,3-diphosphacyclobutane-2,4-diyl reveal several unusual coupling constants together with recognition of the diastereotopicity of the compound. These new data support an uncommon phosphorus-containing molecular structure for the ring system. © 2011 Wiley...
Article
Acid-induced ring expansion of 2H-azaphosphirene complexes 1a−c with HCN is described. These reactions yielded 2H-1,4,2-diazaphosphole complexes 2a−c as a mixture with their κN-coordination isomers 3a−c in different ratios, depending upon the steric demand of the C3-substituent on the diazaphosphole ring. DFT calculations revealed that the isomeriz...
Article
Hydride-induced elimination of resonance stabilized substituents from a phosphorus center of 1,3-diphosphacyclobutane-2,4-diyls leads to the formation of versatile cyclic phosphaallyl anions that are useful for the construction of various electrophile-modified biradical species.
Article
A cyclic phosphaallyl anion generated from a phosphorus-carbon triple bond (phosphaalkyne) was allowed to react with dimethyl- and di-p-tolyl disulfide to afford the corresponding 1,3-diphosphacyclobutane-2,4-diyls bearing the sulfanyl substituent on phosphorus. The sulfanyl-bearing P-heterocyclic biradicals showed high stability permitting easy ha...
Article
The electronic structure and geometry of H2PCSiH3 (1) and (NH2)2PCSiH3 (3) were investigated by extended basis set (DZP) ab initio molecular orbital theory. Both singlet and triplet structures for 1 and 3 are considered. The calculated structure for 11 (ground state) is best characterized as a P-C multiply bonded species with an extremely short (15...
Article
We have succeeded in catenating two sterically encumbered 1,3-di-t-butyl-2,4-bis(2,4,6-tri-t-butylphenyl)-1,3-diphosphacyclobutane-2,4-diyl units with a spacer 1,2-(CH2)2C6H4 to obtain bis(biradicals) as considerably stable compounds. We have discussed physicochemical properties of the dimer, together with DFT calculations of model compounds. Spect...
Article
Interest in stable nucleophilic carbenes has grown rapidly since the isolation of the first "bottle-able" example in 1991. Not only has the structural variation of this class of compounds seen an incredible expansion from laboratories around the world, but the chemical reactivity of these compounds has opened many new opportunities for improvements...
Article
The synthesis of a remarkable cyclic bis(P-H lambda(5)-phosphorane) is reported. A stable phosphorus-heterocyclic biradical, 1,3-diphosphacyclobutane-2,4-diyl, sequentially accepts negatively and positively charged hydrogen atoms to afford 2,4-diphospha-1,3-cyclobutadiene with a diylidic structure containing two P-H bonds.
Article
Two and three stable 1-sec-butyl-2,4-bis(2,4,6-tri-tert-butylphenyl)-1,3-diphosphacyclobutane-2,4-diyl units were catenated to construct multi-biradical derivatives by utilizing 1,3-di-, 1,4-di-, and 1,3,5-trimethylenebenzenes as bridging groups, respectively. UV/Vis spectroscopic and cyclovoltammetric (CV) properties of the multi-biradicals indica...
Article
Atomization energies at 0 K and heats of formation at 0 and 298 K are predicted for diammoniosilane, H(4)Si(NH(3))(2), and its dehydrogenated derivates at the CCSD(T) and G3(MP2) levels. To achieve near chemical accuracy (+/-1 kcal/mol), three corrections were added to the complete basis set binding energies based on frozen core coupled cluster the...
Article
Eine Diradikal-Chromophorbrücke: Di- und Trimethylenphenyl-Einheiten erleichtern eine Wechselwirkung durch den Raum zwischen sterisch anspruchsvollen Diradikaleinheiten (siehe Bild) und damit das Design neuer elektronischer Materialien. In der Festkörperstruktur eines Bis(diradikal)-Derivats stehen zwei Diradikaleinheiten so nahe beieinander, dass...
Article
Various kinds of stable 1,3-diphosphacyclobutane-2,4-diyls, sterically protected by bulky Mes* (2,4,6-tri-t-butylphenyl) groups, were prepared from Mes*-phosphaethyne. The structures and physical and chemical characters were studied. They are discussed in terms of ground-state singlet biradicals and have been confirmed by spectroscopic analyses, X-...
Article
Full-text available
A sterically protected biradical species, 1-tert-butyl-3methyl-2,4-bis(2,4,6-tri-tert-butylphenyl)-1,3-diphosphacyclo- butane-2,4-diyl was allowed to react with tris(4-bromophenyl)ammoniumyl hexachloroantimonate as an oxidant and the product was analyzed by EPR to show that the biradical was oxidized to give the corresponding radical cation species...
Article
The heats of formation of N(2)H, diazene (cis- and trans-N(2)H(2)), N(2)H(3), and hydrazine (N(2)H(4)), as well as their protonated species (diazenium, N(2)H(3)(+), and hydrazinium, N(2)H(5)(+)), have been calculated by using high level electronic structure theory. Energies were calculated by using coupled cluster theory with a perturbative treatme...
Article
Treatment of (TptBu,Me)YbE(thf) (E=I (1), CH2SiMe3 (2)) with tetramethylimidazol-2-ylidene (ImMe4) resulted in very different outcomes depending on the nature of the anionic ligand E. ImMe4 acts as a simple Lewis base toward 1 resulting in substitution of the thf (tetrahydrofuran) ligand and formation of (TptBu,Me)YbI(ImMe4) (3). However, reaction...
Article
Radikal stabil: Ein äußerst stabiles P-heterocyclisches organisches Radikal lieferte die Oxidation eines sterisch belasteten 1,3-Diphosphacyclobutenylanions, das aus Mes*CP (Mes*=2,4,6-tBu3C6H2) erzeugt wurde. Die röntgenographisch ermittelte Struktur des 1,3-Diphosphacyclobuten-4-yl-Radikals ist vergleichbar mit Daten, die aus einer EPR-Analyse un...