Feliu Maseras

Feliu Maseras
ICIQ Institute of Chemical Research of Catalonia | ICIQ

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309
Publications
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15,563
Citations
Citations since 2016
76 Research Items
5897 Citations
20162017201820192020202120220200400600800
20162017201820192020202120220200400600800
20162017201820192020202120220200400600800
20162017201820192020202120220200400600800

Publications

Publications (309)
Article
In previous work we reported the formal synthesis of the marine macrolide (−)-callyspongiolide through a synthetic approach in which the generation of the key macrocyclic core relies on a ruthenium-catalyzed ring-closing metathesis reaction. However, besides the predicted macrolactone intermediate, an undesired cyclooctene was observed. We investig...
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The direct functionalization of Si-H bonds by the nitrene insertion methodology is described. A copper(I) complex bearing a trispyrazolylborate ligand catalyzes the transfer of a nitrene group from PhI═NTs to the Si-H bond of silanes, disilanes, and siloxanes, leading to the exclusive formation of Si-NH moieties in the first example of this transfo...
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We have recently developed a method for the synthesis of pyrrolidines and piperidines via intramolecular C-H amination of N-fluoride amides using [Tp x CuL] complexes as precatalysts [Tp x = tris(pyrazolyl)borate ligand and L = THF or CH3CN]. Herein, we report mechanistic studies on this transformation, which includes the isolation and structural c...
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Cooperative multimetallic catalysis is a fascinating field of research further expanding the role of homogeneous catalysis. The simultaneous activation of two substrates or functionalities by different catalytic entities and their subsequent coupling are the responsible for the rate acceleration and selectivity exerted by these systems. The nature...
Article
The interaction of N‐heterocyclic carbene (NHC) ligands with transition metal centers is analyzed with a set of descriptors derived from the statistical treatment of density functional theory (DFT) computational results. These descriptors, labeled as hidden descriptors (HD), had been previously defined in our group and here are applied with the hel...
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The reactions of dppf-nickel(0) with alkyl halides proceed via three-coordinate nickel(0) intermediates of the form [Ni(dppf)(L)]. The effects of the identity of the added ligand (L) on catalyst speciation and the rates of reactions of [Ni(COD)(dppf)] with alkyl halides have been investigated using kinetic experiments and density functional theory...
Article
Mechanochemistry is an emerging field with many potential applications in sustainable chemistry. But despite the growing interest on the field, its underlying mechanistic foundations are not fully understood yet. This work presents the application of computational tools, such as DFT calculations in continuum and microkinetic modeling, to the analys...
Article
The potential access to Co IV species for promoting transformations that are particularly challenging at Co III still remains underexploited in the context of Cp*Co‐catalyzed C–H functionalization reactions. Herein, we disclose a combined experimental and computational strategy for uncovering the intermediacy of Cp*Co IV species in a Cp*Co‐mediated...
Article
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Many transition-metal complexes MLn decompose diazo compounds N2═CR1R2 generating metal-carbenes LnM═CR1R2 which transfer the carbene group to other substrates, constituting an important tool in organic synthesis. All previous reports have shown that the CR1R2 fragment at the metal-carbene remains intact from the parent diazo compound. Herein we re...
Article
The joint application of experimental and computational approaches discloses unprecedented mechanistic intricacies associated to Cp*Co‐catalyzed C−H functionalization reactions when using nucleophilic coupling partners. The use of trifluoromethylthiolation reveals an exceptional reductive elimination event from high‐valent Cp*CoIV that can be promo...
Chapter
Computational chemistry has made a significant contribution to the understanding of the mechanism of asymmetric hydrogenation by homogeneous transition metal catalysis, and its main contributions are discussed in this chapter. Both asymmetric hydrogenation and transfer hydrogenation catalysts are described. The computational methods for the charact...
Article
The high-spin (S = 5/2) meridional diastereoisomer of [FeIII(tpena)]2+ (tpena = N,N,N'-tris(2-pyridylmethyl)ethylendiamine-N'-acetate), mer-[Fe(tpena)]2+, undergoes photolytic CO2 release to produce an iron(II) intermediate of a radical dihydroimidazopyridine ligand (L•). The structure of this unprecedented transient iron(II)(L•) complex is support...
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Photoelectrochemical cells that utilize water as a source of electrons are one of the most attractive solutions for the replacement of fossil fuels by clean and sustainable solar fuels. To achieve this, heterogeneous water oxidation catalysis needs to be mastered and properly understood. The search continues for a catalyst that is stable at the sur...
Chapter
Photoactivated processes play an increasingly important role in chemistry. Their widespread use is still relatively recent, and the application of computational methods to the treatment of the large systems usually involved in experimentally relevant systems is even more recent. The application of TD-DFT calculations for the photoactivation step an...
Article
Under silver catalysis conditions, using [Tp*,BrAg]2 as the catalyst precursor, allenes react with PhI=NTs in the first example of efficient metal-mediated intermolecular nitrene transfer to such substrates. The nature of the substituent at the allene seems crucial for the reaction outcome since arylallenes are converted into azetidine derivatives...
Article
DFT calculations and microkinetic simulations are applied to the reproduction of previously reported experimental results on the evolution of product concentration versus time in the condensation reaction of n-butylamine and benzaldehyde. The mechanism is complicated by the role played by water impurities as proton shuttles. Several functionals and...
Article
The first approach to a quantitative model to calculate nucleophilicity of alkanes is reported. A statistical treatment is applied to the analysis of the reactivity of twenty‐nine different alkane C‐H bonds toward in situ generated metal‐carbene electrophiles. The correlation of the recently reported experimental reactivity with two different sets...
Article
Das QDEAN‐Modell stellt einen ersten Ansatz zur quantitativen Modellierung der Reaktivität von Alkan‐C‐H‐Bindungen gegenüber Elektrophilen dar. Eine bemerkenswerte Korrelation zwischen experimentellen und berechneten Werten wurde mit nur sechs topologischen Deskriptoren für die untersuchten C‐H‐Bindungen erreicht. Abstract A first quantitative mod...
Article
The reaction between bromobenzene and palladium(0) complexes leading to a palladium(II) complex containing bromide and phenyl ligands is studied computationally with DFT methods. Three different mechanisms are considered: concerted, nucleophilic substitution and radical. A systematic analysis is carried out on the effect on each of these mechanisms...
Article
A general protocol for the enantioselective synthesis of 3‐heterosubstituted‐2‐amino‐1‐ols was developed based on metal‐ free intramolecular regio‐ and stereoselective diene aziridination and regioselective opening. Kinetic resolution of the resulting (1′‐NR1R2 and 1′‐SR)‐4‐oxazolidinones was performed using ABCs organocatalysts, expanding the appl...
Article
For the first time, the door to access selectively Cu(CF3)2− have been unlocked. These species, ubiquitous in trifluoromethylation reactions, displayed a superior reactivity towards aryl halides than its argentate and aurate congeners. Merging experimental and computational approaches, a complex mechanistic scenario is unraveled, through a CuI/III...
Article
The organocatalyzed synthesis of the Wieland‐Miescher ketone (WMK) via N‐sulfonyl‐binamprolinamide catalysis was investigated using experimental and computational tools. A mechanistic proposal is presented describing the origin of the high enantioselectivity, which rivals that of aldolases. The computational study reveals that the role of the proli...
Article
N-Heterocyclic carbene catalysts are used for the first time to mediate asymmetric [8 + 2] cycloadditions of enals with tropones. The kinetic [8 + 2] cis-cycloadducts can be epimerized to their trans analogues by simply using increased amounts of base and longer reaction times. Substituted tropones are also tolerated, and the cycloaddition products...
Article
The dual function of the N‐F bond as an effective oxidant and subsequent nitrogen source in intramolecular aliphatic C‐H functionalization reactions is explored. Copper catalysis is demonstrated to exercise full regio‐ and chemoselectivity control, which opens new synthetic venues to nitrogenated heterocycles with predictable ring size. For the fir...
Article
The dual function of the N‐F bond as an effective oxidant and subsequent nitrogen source in intramolecular aliphatic C‐H functionalization reactions is explored. Copper catalysis is demonstrated to exercise full regio‐ and chemoselectivity control, which opens new synthetic venues to nitrogenated heterocycles with predictable ring size. For the fir...
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Full-text available
The presence of single-electron transfer (SET) steps in water oxidation processes catalyzed by first-row transition metal complexes has been recently recognized, but the computational characterization of this type of process is not trivial. We report a systematic theoretical study based on density functional theory (DFT) calculations on the reactiv...
Article
Despite the known nucleophilic nature of [M(CF 3 ) 2 ] ⁻ (M=Cu, Ag, Au) complexes, their participation in trifluoromethylation reactions of aryl halides remains unexplored. Here, for the first time, selective access to a [Cu(CF 3 ) 2 ] ⁻ species is reported, which is ubiquitous in Cu-mediated trifluoromethylations, and we rationalize its complex me...
Article
The computational characterization of the full catalytic cycle for the synthesis of indoline from the reaction between a iodoacetanilide and an alkene catalyzed by a combination of a nickel complex and a photoactive ruthenium species is presented. A wide variety of oxidation states of nickel, as many as four, Ni(0), Ni(I), Ni(II) and Ni(III), is sh...
Article
The computational characterization of the full catalytic cycle for the synthesis of indoline from the reaction between a iodoacetanilide and an alkene catalyzed by a combination of a nickel complex and a photoactive ruthenium species is presented. A wide variety of oxidation states of nickel, as many as four, Ni(0), Ni(I), Ni(II) and Ni(III), is sh...
Article
The efficiency of the OPBA‐Cu (OPBA= tetraaanionic derivative of 1,2‐phenylene bis(oxamic acid)) water oxidation catalyst family has been studied by DFT calculations. We have explored four different tetraamidate copper complexes [(L1‐4)Cu]2‐ (where L1 is N1,N1'‐(1,2‐phenylene)bis(N2‐methyloxalamidate) and L2‐4 are variations of the same ligand with...
Article
The ONIOM method, developed in the group of Keiji Morokuma, is one of the most successful examples of quantum mechanics / molecular mechanics (QM/MM) treatments, and of multilayer methods in general. Its implementation in the Gaussian program package is in particular widely used. This implementation has access to the wide variety of QM methods avai...
Article
A statistical treatment of the DFT-computed heterolytic bond dissociation energies (BDE) between a diverse variety of metal fragments and ligands leads to the identification of five hidden descriptors that best characterize the bonding ability per moiety, and of a simple mathematical formula able to obtain from these hidden descriptors a BDE estima...
Article
The performance of a thermodynamic cycle for the calculation of the standard reduction potential (SRP) of a series of metals is examined. It is found that the introduction of simple entropic corrections substantially improves the agreement with experimental data. The accuracy of the estimations is in the range of 0.04 V, which opens the possibility...
Article
The iron(III) complex [Fe(tpena)]2+ (tpena = N, N, N'-tris(2-pyridylmethyl)ethylendiamine- N'-acetate) undergoes irreversible O2-dependent N-demethylcarboxylation to afford [FeII(SBPy3)(MeCN)]2+ (SBPy3 = N, N-bis(2-pyridylmethyl)amine- N-ethyl-2-pyridine-2-aldimine), when irradiated with near-UV light. The loss of a mass equivalent to the glycyl gr...
Article
The relative reactivity of a series of alkane C−H bonds towards silver, copper, and rhodium carbene complexes acting as electrophiles has been studied. In their Communication on page 13848 ff., P. J. Pérez and co‐workers show that the carbon–hydrogen bond of methane represents the poorest nucleophile and, therefore, sits on top of the ladder. The o...
Article
Die relative Reaktivität der C‐H‐Bindungen von Alkanen als Nucleophile gegenüber mehreren Silber‐, Kupfer‐ und Rhodium‐Carben‐Komplexen als starke Elektrophile wurde untersucht. In ihrer Zuschrift (DOI: 10.1002/ange.201807448) zeigen P. J. Pérez et al., dass die C‐H‐Bindung von Methan das schwächste Nucleophil ergibt und sich daher auf der Treppe g...
Article
The ONIOM scheme is one of the most popular QM/MM approaches, but its extended application has been so far hindered by the limited availability of force fields in most practical implementations. This paper describes a simple software code to overcome this limitation, and its application to three representative chemical problems. The "Shell Interfac...
Article
This work addresses a counterintuitive observation in the reactivity of the well-known ruthenium complexes [Ru(X)H(CO)(PiPr3)2], according to which the 5-coordinate chloro complex (X = Cl, 1) is less reactive toward phenylacetylene than its 6-coordinate acetate analogue (X = κO2-OC(O)Me, 3), since 3 undergoes a hydride-to-alkenyl-to-alkynyl transfo...
Article
We report quantitative measurements of the relative reactivities of a series of C−H bonds of gaseous or liquid CnH2n+2 alkanes (n=1–8, 29 different C−H bonds) towards in situ generated electrophiles (copper, silver, and rhodium carbenes), with methane as the reference. This strategy surpasses the drawback of previous model reactions of alkanes with...
Article
We report quantitative measurements of the relative reactivities of a series of C−H bonds of gaseous or liquid CnH2n+2 alkanes (n=1–8, 29 different C−H bonds) towards in situ generated electrophiles (copper, silver, and rhodium carbenes), with methane as the reference. This strategy surpasses the drawback of previous model reactions of alkanes with...
Article
A combined experimental and computational approach has been used to shed light on the mechanism of the Pd-catalyzed oxidative homocoupling of alkynes using oxygen as oxidant. Mechanistic understanding is important because of the synthetically relevant direct involvement of oxygen in the oxidative coupling, and because of the presence of related pro...
Article
Organosilver(I) species have previously demonstrated their potential as coupling partners in Pd‐catalyzed transformations, but this ability is far from being fully exploited. Discrete “AgCF3” complexes with a new silver ate complex, (Cs)[Ag(CF3)2], have been employed in the highlighted paper. Their unique structure can tackle some usually overshado...
Article
Computational homogeneous catalysis has focused traditionally on the calculation of free energy barriers, which are ultimately related to rate constants. Experiments do not focus on rate constants, but on reaction rates, which depend also on concentrations. The increasing efficiency of DFT and other electronic structure techniques has led to the de...
Article
Full-text available
The mechanism of a trinuclear cooperative dehydrogenative C‐N bond forming reaction is investigated in this work, which avoids the use of chelate assisting directing groups. Two new highly efficient Ru/Cu co‐catalyzed systems were identified, allowing three orders of magnitude greater TOFs than the previous state of the art. In‐depth kinetic studie...
Article
This work describes the employment of discrete "AgCF3 " complexes as efficient transmetalating agents to PdII to surmount overlooked challenges related to the transmetalation step in Pd-catalyzed trifluoromethylation processes. We report the participation of a unique silver ate (Cs)[Ag(CF3 )2 ] complex, under stoichiometric and catalytic conditions...
Article
Full-text available
The photocatalyzed insertion of dioxygen into the Pt(II)-methyl bond in terpyridine platinum complexes has been shown to proceed efficiently, but its mechanism remains a challenge. In particular, there are serious counter-intuitive differences in the reactivity of structurally similar complexes. M06 calculations in solvent with a valence double-zet...
Article
Density functional theory calculations are applied to the study of a cycloaddition reaction between phenyl acetylene and phenyl azide taking place inside a self‐assembled nanoreactor derived from the coupling of two resorcinarene‐derived units. Calculations are applied to all steps in the reactivity of the system: self‐assembly, guest trapping, gue...
Article
A modular approach employing indene as common starting material, has enabled the straightforward preparation in three reaction steps of P-thioether ligands for the Pd-catalyzed asymmetric allylic substitution. The analysis of a starting library of P-thioether ligands based on rational design and theoretical calculations has led to the discovery of...
Article
Nickel catalysis is gaining in popularity in recent years, mostly within the area of cross-coupling. However, unlike Pd, the mecha-nisms of Ni-catalyzed C-C and C-heteroatom bond forming reactions have been much less studied, in particular when N-heterocyclic carbenes are used as ligands. Here, we present a thorough study into the mechanism of C-N...
Article
DFT calculations are applied to the study of the oxidative coupling between benzoic acid and 1-phenyl-1-propyne catalyzed by [CpRhCl2]2 using either Cu(OAc)2(H2O) or Ag(OAc) as terminal oxidants, a process that has been experimentally shown to have subtleties related to regioselectivity (placement of the phenyl substituent of the alkyne in the isoc...
Article
Regio‐ and stereoselective oxyamination of dienes through a tandem rhodium‐catalysed aziridination–nucleophilic opening affords racemic oxazolidinone derivatives, which undergo a kinetic resolution acylation process with amidine‐based catalysts (ABCs) to achieve s values of up to 117. This protocol was applied to the enantioselective synthesis of s...
Article
Full-text available
An efficient protocol was developed to construct functionally dense quaternary carbons with concomitant formation of a new Csp3-Csp3 bond via Pd-catalyzed decarboxylative transformation of vinyl cyclic carbonates. This redox neutral catalytic system features stereocontrolled formation of multi-substituted allylic scaffolds with an aldehyde function...
Article
The result of the application of different approaches based on the ideal gas/rigid rotor/harmonic oscillator (IGRRHO) model, commonly used in popular software packages, for the calculation of free energies in solution is compared with that of ab initio molecular dynamics for a process involving ligand exchange in palladium complexes. The IGRRHO-bas...
Article
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The reduction of aryl azides in the absence of an obvious reducing agent is reported. Careful catalyst design led to the production of anilines in the presence of water and air. The reaction medium (toluene/water) is crucial for the success of the reaction, as DFT calculations support the formation of benzyl alcohol as the oxidation product. A sing...
Article
Oxidative coupling reactions, where two electrons are released from the reactants and trapped by an oxidant, have arisen as a versatile alternative to cross-coupling in chemical synthesis. Despite the large number of experimental reports on the process, a clear mechanistic picture is only starting to emerge. In this perspective, we highlight the co...
Article
Alkyne FunctionalizationIn their Communication on page 12842 ff., F. Maseras, M. M. Díaz-Requejo, P. J. Pérez et al. report the copper-catalyzed reaction of alkynes and the nitrene precursor PhI=N-Ts (Ts=p-toluenesulfonyl).
Article
AlkinfunktionalisierungIn ihrer Zuschrift auf S. 13022 ff. berichten F. Maseras, M. M. Díaz-Requejo, P. J. Pérez et al. über die Kupfer-katalysierte Reaktion von Alkinen mit der Nitren-Vorstufe PhI=N-Ts (Ts=p-Toluolsulfonyl).
Article
The computational characterization of the mechanism for complex reactions involving the photoactivation of transition metal compounds remains a challenge for theoretical chemistry. In this work we show how the application of DFT and ONIOM(DFT:MM) methods can characterize the photoinduced iridium-catalyzed enantioselective trichloromethylation of 2-...
Article
A novel transformation is reported for the reaction of terminal or internal alkynes with the nitrene precursor PhI=NTs (Ts = p-toluenesulfonyl) in the presence of catalytic amounts of TpBr3Cu(NCMe) (TpBr3 = hydrotris(3,4,5-tribromo-pyrazolylborate). Two products containing an imine functionality have been isolated from the reaction mixtures, identi...
Article
A novel transformation is reported for the reaction of terminal or internal alkynes with the nitrene precursor PhI=NTs (Ts = p-toluenesulfonyl) in the presence of catalytic amounts of TpBr3Cu(NCMe) (TpBr3 = hydrotris(3,4,5-tribromo-pyrazolylborate). Two products containing an imine functionality have been isolated from the reaction mixtures, identi...
Article
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The intermolecular gold(I)-catalyzed reaction between arylalkynes and alkenes leads to cyclobutenes by a [2 + 2] cycloaddition, which takes place stepwise, first by formation of cyclopropyl gold(I) carbenes, followed by a ring expansion. However, 1,3-butadienes are also formed in the case of ortho-substituted arylalkynes by a metathesis-type proces...
Article
We have combined the AMOEBA09 polarizable force field with the ONIOM(QM:MM) method to rationalize binding energies and binding preferences of the OH, HCO, and CH3 radicals on crystalline water ice (Ih). ONIOM(M062X:AMOEBA09) and ONIOM(wB97XD:AMOEBA) calculations suggest that the dangling hydrogen (d-H) or dangling oxygen (d-O) on the binding sites...
Article
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The reaction of carbon dioxide with α-siloxy silanes assisted by cesium fluoride is studied by means of DFT calculations with the B97D functional. Different mechanistic models are examined, including explicit introduction of cationic counterions and solvent molecules. The reaction is confirmed to proceed through carbanionic intermediates generated...
Article
A photochemical organocatalytic strategy for the direct enantioselective β-benzylation of α,β-unsaturated aldehydes is reported. The chemistry capitalizes upon the light-triggered enolization of 2-alkyl-benzophenones to afford hydroxy-o-quinodinomethanes. These fleeting intermediates are stereoselectively intercepted by chiral iminium ions, transie...
Article
Full-text available
A photochemical organocatalytic strategy for the direct enantioselective β-benzylation of α,β-unsaturated aldehydes is reported. The chemistry capitalizes upon the light-triggered enolization of 2-alkyl-benzophenones to afford hydroxy-o-quinodinomethanes. These fleeting intermediates are stereoselectively intercepted by chiral iminium ions, transie...
Article
Silver(I) promotes the highly chemoselective N-amidation of tertiary amines under catalytic conditions to form aminimides by nitrene transfer from PhI=NTs. Remarkably, this transformation proceeds in the presence of olefins and other functional groups without formation of the commonly observed aziridines or C-H insertion products. The methodology c...
Article
The systematic computational study of the mechanism for water oxidation in four different complexes confirms the existence of an alternative mechanism for the O-O bond formation step to those previously reported: the single electron transfer - water nucleophilic attack (SET-WNA). The calculated mechanism relies on two SET steps, and features the ex...