José Alemán

José Alemán
Universidad Autónoma de Madrid | UAM · Department of Organic Chemistry, Institute for Advanced Research in Chemical Sciences (IAdChem), Universidad Autónoma de Madrid, 28049 Madrid, Spain.

Professor

About

261
Publications
18,243
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5,848
Citations
Citations since 2016
127 Research Items
3413 Citations
20162017201820192020202120220100200300400500600
20162017201820192020202120220100200300400500600
20162017201820192020202120220100200300400500600
20162017201820192020202120220100200300400500600
Additional affiliations
January 2009 - present
Universidad Autónoma de Madrid
Position
  • Professor (Associate)

Publications

Publications (261)
Chapter
In this chapter, we have summarized catalytic systems based on the combination of photocatalytic processes with organocatalysis, paying special attention to the activation mode. In the covalent catalysis section, we show the blend between iminium ion and enamine with photoredox processes, using an external photocatalyst. In addition, in absence of...
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Correction for ‘Metal–organic framework (MOF)-, covalent-organic framework (COF)-, and porous-organic polymers (POP)-catalyzed selective C–H bond activation and functionalization reactions’ by Saba Daliran et al. , Chem. Soc. Rev. , 2022, https://doi.org/10.1039/d1cs00976a.
Article
Although C-H functionalization is one of the simplest reactions, it requires the use of highly active and selective catalysts. Recently, C-H-active transformations using porous materials such as crystalline metal-organic frameworks (MOFs) and covalent-organic frameworks (COFs) as well as amorphous porous-organic polymers (POPs) as new emerging hete...
Article
The immobilization of TiO2 nanoparticles on graphene acid (GA), a conductive graphene derivative densely functionalized with COOH groups, is presented. The interaction between the carboxyl groups of the surface and the titanium precursor leads to a controlled TiO2 heterogenization on the nanosheet according to microscopic and spectroscopic characte...
Article
We present the design and synthesis of a new covalent triazine framework with high content of N atoms bearing triazine and phenanthroline moieties. This material displays interesting luminescence phenomena and enhanced photoredox activity as a consequence of synergistic combination of both N-containing aromatic fragments. As catalytic application,...
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Nanomanipulation of molecular materials such as carbon nanotubes (CNTs) or new covalent organic frameworks (COFs) is key not only for the study of their fundamental physicochemical properties, but also for building and probing nanodevices. Therefore, we have investigated the tribological properties of oxidized MWCNTs (ox-MWCNTs) and their hybridiza...
Article
A nickel‐catalysed reductive cross‐coupling reaction between benzyl sulfonium salts and benzyl bromides is reported. Simple, stable and readily available sulfonium salts have shown their ability as leaving groups in cross electrophile coupling, allowing the formation of challenging sp3‐sp3 carbon‐carbon bonds, towards the synthesis of interesting d...
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The photocatalytic generation of α-amino radicals is combined with chiral isothiourea derived α,β-unsaturated acyl ammonium intermediates. The reaction proceeds via a [3+2] radical-polar crossover mechanism to generate γ-lactams in good...
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The activation of molecules through intramolecular hydrogen-bond formation to promote chemical reactions appears as a suitable strategy in organic synthesis, especially for the preparation of chiral compounds under metal and organocatalytic conditions. The use of this interaction has enabled reactivity enhancement of reagents, as well as stabilizat...
Article
A simple one-step synthesis of a heterogeneous photocatalyst based on the encapsulation of the quinolinate-platinum complex 1 in the inner cavity of Single Walled Carbon Nanotubes ([email protected]) is presented. This strategy generates a robust and stable catalyst for photooxidations performed in water media. [email protected] is characterized sp...
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Herein, we report, a general, facile and environmentally friendly Minisci-type alkylation of N-heteroarenes under simple and straightforward electrochemical conditions using widely available alkyl halides as radical precursors. Primary, secondary and tertiary alkyl radicals have been shown to be efficiently generated and coupled with a large variet...
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Glass-forming ability is one of the most desired properties of organic compounds dedicated to optoelectronic applications. Therefore, finding general structure–property relationships and other rules governing vitrification and related near-glass-transition phenomena is a burning issue for numerous compound families, such as Schiff bases. Hence, we...
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Herein, we report the enantioselective addition of remote alkyl radicals, generated from the ring opening of unstrained cycloalkanols by a proton-coupled electron transfer (PCET) process, to 2-acyl imidazoles previously coordinated to a rhodium-based chiral Lewis acid. High yields and enantioselectivites up to 99% are achieved in 1 h. Mechanistic i...
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Three materials containing a photoactive unit, 10-phenyl phenothiazine (PTH), have been studied for the visible light-mediated oxidative coupling of amines. In particular, the materials considered are assembled through the condensation of extended polyimine, polyhydrazone, or polytriazine frameworks. These three materials present different stabilit...
Article
The application of proton coupled electron transfer (PCET) processes in organic synthesis has opened the door to new radical intermediates for synthesis such as alkyl radicals in remote positions to a ketone. Herein, we present the addition of these remote alkyl radicals to electron deficient double bonds under photoorganocatalyzed and very mild co...
Article
A sustainable strategy for the alkylation of heterocycles is presented. The protocol relies on the in-situ generation and further in-line use of alkyl zinc sulfinates through a continuous-flow system. The...
Article
The carbocatalytic synthesis of azines (N-N linked diimines) by mild-oxidized multiwalled carbon nanotubes catalyst (oxMWNT) is presented. The material, just with a 5 %wt. loading, is able to carry out a smooth room-temperature metal-free condensation of aldehydes and hydrazine, without external additives, to obtain a wide library of symmetric and...
Article
Herein, a visible-light mediated strategy unlocking a family of cyclic β-amino carbonyl derivatives bearing three contiguous stereogenic centres is introduced. The overall reactivity relies on the performance of the substrate-catalyst...
Article
The generation of sulfonyl radicals has long been known as a flexible strategy in a widespread of different sulfonylative transformations. Meanwhile their use in alkylation processes has been somehow limited due to their inherent difficulty in evolving to less-stable radicals after sulfur dioxide extrusion. Herein we report a convenient strategy th...
Article
The generation of sulfonyl radicals has long been known as a flexible strategy in a widespread of different sulfonylative transformations. Meanwhile their use in alkylation processes has been somehow limited due to their inherent difficulty in evolving to less-stable radicals after sulfur dioxide extrusion. Herein we report a convenient strategy th...
Preprint
Full-text available
Herein, we report, for the first time, a general, facile and environmentally friendly Minisci-type alkylation of N -heteroarenes under simple and straightforward electrochemical conditions using widely available alkyl halides as radical precursors. Primary, secondary and tertiary alkyl radicals have shown to be efficiently generated and coupled wit...
Article
α-Aminoamides are a reiterative molecular subunit in transcendental molecules which bear attractive functionalities for (bio)synthetic purposes. Herein, their preparation harnessing photocatalysis in flow is described, providing significant improvements over other...
Article
The phenanthroline unit in an imine-based covalent organic framework (Phen-COF) offers a robust coordination site for Pd(OAc)2 centers. Coordination of palladium centers is demonstrated by a variety of techniques, including X-ray photoelectron spectroscopy and total X-ray fluorescence. The stable phenanthroline-Pd(II) coordination avoids leaching o...
Article
Mixtures of triphenylamine (TPA) and phenyl phenothiazine (PTH) fragments have been incorporated into a series of extended polyimine structures that have been applied in the photodegradation of pollutants of different nature under visible light irradiation. Results obtained revealed that materials containing PTH as the sole photoactive unit resulte...
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Reaction between concentrated solutions of phenotiazine containing trialdehyde building block 4,4′,4″-(10-phenothiazine-3,7,10-triyl)tribenzaldehyde and (1R,2R)-cyclohexane-1,2-diamine results in the formation of a yellow transparent film. Exhaustive characterization of this material indicates that it is the result of the assembly of a linear polym...
Article
A combination of quantum computations with calorimetric, dielectric, infrared, and diffraction studies was used to dissect the nature of atypical bifurcated (three-centered) hydrogen bonds (BHBs). Based on the analysis of four glass-forming Schiff bases, this article experimentally proves that self-organization via BHBs may be prevalent in H-bondin...
Article
A highly enantioselective vinylogous Mukaiyama aldol reaction to ketoesters catalysed by a hydrogen-bond-donor based bifunctional organcatalysts is presented. The addition of silyloxy dienol ether gives rise to multifuncional chiral tertiary alcohols bearing a versatile α,β-unsaturated aldehyde with an excellent enantiocontrol.
Article
A half‐sandwich ruthenium‐ p ‐cymene organometallic complex has been stepwise immobilized at Single Walled Carbon Nanotubes (SWNT) sidewalls through covalent chemistry. The introduction of amino groups by means of diazonium‐chemistry protocols leads the grafting at the outer walls of the nanotubes. This hybrid material is active in the transfer hyd...
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The functionalization of an imine-based layered covalent organic framework (COF), containing phenanthroline units as ligands, has allowed the obtention of a heterobimetallated material. Photoactive Ir and Ni fragments were immobilized within the porous structure of the COF, enabling heterogeneous light-mediated Csp³–Csp² cross-couplings. As radical...
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A highly efficient enantioselective inverse-electron-demand aza-Diels–Alder reaction between aza-sulfonyl-1-aza-1,3-butadienes and silyl (di)enol ethers has been developed. The presented methodology allows the synthesis of benzofuran-fused 2-piperidinol derivatives with three contiguous stereocenters in a highly selective manner, as even the hemiam...
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A highly regio- and enantioselective vinylogous Mukaiyama-type reaction for the dearomatization of quinazolines and other heteroarenes under anion-binding catalysis is presented.
Article
Inverse‐electron‐demand hetero‐Diels‐Alder reactions have been an important breakthrough for the synthesis of heterocyclic compounds. Among all their variants, the organocatalytic enantioselective version has been widely explored since the asymmetric construction of diversely functionalized scaffolds under reaction conditions encompassed within the...
Article
The application of organic photocatalysts towards the oxidation of pollutants in water is hampered by different limitations such as their insolubility in the media. Herein, we report that the grafting of a photo-organocatalyst into mesoporous silica materials is an ideal approach to obtain effective catalysts. Thereby, the photocatalyst 10-phenylph...
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A highly enantioselective protocol has been recently described as allowing the synthesis of five-membered cyclic imines harnessing the selective generation of a β-Csp3-centered radical of acyl heterocyclic derivatives and its subsequent interaction with diverse NH-ketimines. The overall transformation represents a novel cascade process strategy cra...
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Herein, an asymmetric organocatalytic aza-Michael addition reaction of ketimines to nitroolefins is presented. The use of 2-hydroxybenzophenone imine improves the enantioselective addition of N-centered nucleophiles to nitroalkenes by means of intramolecular hydrogen bond formation at the imine moiety. Moreover, the versatility of the process is de...
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The strategies for sustainability and competitiveness of the biodiesel industry may be improved by adding value through co-products, especially for novel biodegradable products from non-edible vegetable oils. In this study, the chemical modifications of ricinoleic acid obtained from castor oil were performed to obtain biodegradable base stock oils....
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Cycloaddition reactions, in particular Diels‐Alder reactions, have attracted a lot of attention from organic chemists since they represent one of the most powerful methodologies for the construction of carbon‐carbon bonds. In particular, inverse‐electron‐demand hetero‐Diels‐Alder reactions have been an important breakthrough for the synthesis of he...
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Covalent Organic Frameworks (COFs) and related extended organic materials have been widely used as photocatalysts in the last few years. Such interest arises from the wide range of covalent linkages employed in their construction, which offer many possibilities to design extended frameworks and to link photoactive building blocks. Thus, the potenti...
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When aiming to build molecules with elevated molecular complexity starting from relatively simple starting materials, photochemical transformations represent an open avenue to circumvent analogous multistep procedures. Specifically, light‐mediated cycloadditions remain as powerful tools to generate new bonds begotten from non‐very intuitive disconn...
Article
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New 1,2-azolylamidino complexes cis-[Ru(bipy)2(NH═C(R)az*-κ2N,N)](OTf)2 (R = Me, Ph; az* = pz, indz, dmpz) are synthesized via chloride abstraction after a subsequent base-catalyzed coupling of a nitrile with the previously coordinated 1,2-azole. The synthetic procedure allows the easy obtainment of complexes having different electronic and steric...
Article
The asymmetric synthesis of chiral polycyclic ethers by an intramolecular [2+2] photocycloaddition is described. This process proceeded through a photocatalitically active iminium ion-based charge transfer (CT) complex under visible light...
Article
In the present work, a light‐driven, atom‐economical strategy that unlocks access to enantioenriched substituted chiral 1‐pyrroline derivatives is introduced. The methodology lays in the distal functionalization of acyl heterocycles enabling a hydrogen atom transfer (HAT) and the use of tailored made ketimines as reliable electrophilic partners. Th...
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An atom‐economical strategy has been developed for the visible‐light‐driven synthesis of enantioenriched substituted 1‐pyrroline derivatives with wide functional‐group tolerance (see scheme). In this enantioselective radical approach, stereoselectivity was dictated by coordination to a chiral‐at‐rhodium catalyst, and water was produced as the only...
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The broad presence of azaarene moieties in natural products has promoted the development of new functionalization reactions, giving access to larger libraries of bioactive compounds. The light promoted [2 + 2] photocycloaddition reaction to generate cyclobutanes has been extensively studied in photochemistry. In particular, De Mayo reported the [2...
Article
In this work, we describe the use of visible light and a photocatalytic system for the cyclization of iodoaryl vinyl derivatives to tetrahydroquinoline structures. The reaction proceeds under very mild conditions, tolerates different functional groups and more importantly, the method allows the synthesis of N‐free tetrahydroquinolines from N‐unprot...
Article
A sustainable synthesis of isothiazoles has been developed using an α-amino-oxy acid auxiliary and applying photoredox catalysis. This simple strategy features mild conditions, broad scope and wide functional group tolerance representing a new enviromentally friendly option to prepare these highly valuable heterocycles. Furthermore, the synthetic v...
Article
A sustainable synthesis of isothiazoles has been developed using an α-amino-oxy acid auxiliary and applying photoredox catalysis. This simple strategy features mild conditions, broad scope and wide functional group tolerance representing a new enviromentally friendly option to prepare these highly valuable heterocycles. Furthermore, the synthetic v...
Article
Cationic Pt(II) complexes ([Pt(QO/S)(P∧P)]X), having 8-oxy or 8-thioquinolinate (QO/S) and seven different mono- or bidentate phosphines as ligands, have been synthesized and characterized. The photophysical, stability, and photocatalytic properties of those complexes were studied and compared to that of the parent [Pt(QO/S)(dmso)(Cl)]. The coordin...
Article
In the last years, an increasing interest towards the development of novel enantioselective strategies in photocatalysis has been observed within the research community. The high challenge associated with the intrinsic nature of photochemical reactions has obstructed a fast development of this research field in comparison with asymmetric thermal pr...
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A novel, on‐surface synthesis of oligomers of meta‐polyaniline from para‐aminophenol precursors by an unexpected formal 1,4 Michael‐type addition at the meta position is reported. Experimental and theoretical results show that the reaction proceeds via a highly specific interaction between the precursor and the Pt surface that induces the reduction...
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On‐surface synthesis is emerging as a highly rational bottom‐up methodology for the synthesis of molecular structures that are unattainable or complex to obtain by wet chemistry. Here, oligomers of meta‐ polyaniline, a known ferromagnetic polymer, were synthesized from para ‐aminophenol building‐blocks via an unexpected and highly specific on‐surfa...
Cover Page
Catal. Sci. Technol cover page featuring the article: The role of catalyst–support interactions in oxygen evolution anodes based on Co(OH)2 nanoparticles and carbon microfibers
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Among the different alternatives for catalysis using metal–organic frameworks (MOFs) or covalent organic frameworks (COFs), photocatalysis has remarkably evolved during the last decade. Photocatalytic reticular materials allowed recyclability and easy separation of catalyst from the product, also reaching the activity and selectivity commonly obser...
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The innate electrophilicity of imine building blocks has been exploited in organic synthetic chemistry for decades. Inspired by the resurgence in photocatalysis, imine reactivity has now been redesigned through the generation of unconventional and versatile radical intermediates under mild reaction conditions. While novel photocatalytic approaches...
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The electrochemical reduction of organic contaminants allows its removal from water. In this contribution, the electrocatalytic hydrogenation of nitrobenzene is studied using both oxidized carbon fibres and ruthenium nanoparticles supported on unmodified carbon fibres as catalysts. The two systems produce azoxynitrobenzene as main product, while an...
Article
A well-established strategy to synthesize heterogeneous, metal-organic framework (MOF) catalysts that exhibit nanoconfinement effects, and specific pores with highly-localized catalytic sites, is to use organic linkers containing organocatalytic centers. Here, we report that by combining this linker approach with reticular chemistry, and exploiting...
Article
An asymmetric aminocatalytic activation strategy to obtain enantioenriched cyclobutanes through [2+2] photocycloaddition under visible light irradiation is presented. This metal-free process does not require the use of any external photocatalyst, as it is catalyzed by a simple diamine, which upon condensation with an enone substrate, forms an imini...
Article
The performance of OER anodes based on supported nanocatalysts is highly dependent on the interactions taking place at the interface between the nanocatalyst and the employed conductive support. Herein, the versatility offered by the organometallic approach for the synthesis of metal-based nanostructures allowed preparing electrodes of tailored nan...
Article
A new photoactive Pt (II) hydroxyquinoline complex has been covalently linked into the structure of an imine-based layered covalent organic framework (COF) through the monomer truncation strategy. Such strategy allows the incorporation of molecular fragments with only one functional group able to condensate into the imine-framework. The photocataly...
Article
The first enantioselective method for the installation of the SCF3 group at the C-4 position of azlactones is described in the present communication under quinidinium phase transfer catalysis. The higher performance of substrates containing electron-rich 2-aryl groups at the azlactone was rationalized using DFT calculations.
Article
An unprecedented behavior of ortho-sulfinylpropargyl carbanions in the presence of optically active sulfinylimines affords two different families of compounds: this peculiar chemodivergency is importantly affected by the nature of the employed base, and assisted by the configuration of the electrophile, displaying no alteration in the stereocontrol...
Article
The current study presents a direct CF2H radical addition to C=N bonds predicated on the photocatalytic activation of commercially available zinc difluoromethanesulfinate. The mild conditions in place lead to impressive...
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The assembly of 3-dimensional covalent organic frameworks on the surface of carbon nanotubes is designed and successfully developed for the first time via the hybridization of imine-based covalent organic frameworks (COF-300) and oxidized MWCNTs by one-pot chemical synthesis. The resulting hybrid material ox-MWCNTs@COF exhibits a conformal structur...
Article
The first asymmetric α-trifluoromethylthiolation of 2-substituted isoxazolidin-5-ones was developed using Maruoka type N-spiro ammonium catalysts under phase-transfer conditions. The resulting products, containing a trifluoromethylthiolated quaternary chiral carbon, were obtained in moderate to good yields and up to 98:2 enantiomeric ratio. Moreove...
Article
A simple and general conjugate nucleophilic halogenation is presented. The THTO/halosilane combination has shown the ability to act as a nucleophilic halide source in the conjugate addition to a variety...
Article
Non-covalent inclusion of small acid and base molecules (CH3COOH and NEt3) in an imine structure based on micrometre COF-300 crystals and amorphous nanoparticles results on the facile modulation of its acid-base properties. Such strategy results in the triggering of acidic/basic catalytic activity of the otherwise inactive materials towards ring-op...
Article
The intermolecular diastereoselective and enantioselective synthesis of pyrrolo[1,2-a]indoles is developed through a [3+2] cycloaddition between silyl-indole derivatives and alpha,beta-unsaturated N-acyl oxazolidinones by merging photocatalysis and Lewis acid catalysis.
Article
An enantioselective organocatalytic conjugate azidation of α,β‐unsaturated ketones is presented. A bifunctional organocatalyst activates TMSN3, triggering the nucleophilic addition of the azido group to enones in absence of external promoters and avoiding the direct use or the pre‐formation of highly toxic and explosive hydrazoic acid. This protoco...
Article
Photochemistry of extended polyimine COF structures with laminar, spherical and 3D architectures has been examined. We show that these materials, composed by undecorated phenyl rings and imine fragments, can act as photocatalyts in oxidative transformations, being the crystalline laminar material the most active photocatalyst. The sulfoxidation rea...
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Aryl radical generation and manipulation constitutes a long-standing challenge in organic synthesis. Photocatalytic single-electron reduction of aryl halides has been established as a premier activation pathway to reach these intermediates. The current study integrates the conceptual simplicity of the classical intramolecular homolytic substitution...
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The most useful strategies for the alkylation of allylic systems are related to the Tsuji-Trost reaction or the use of different Lewis acids. Herein we report a photocatalytic approach for the allylation reaction of a variety of nucleophiles, such as heteroarenes, amines and alcohols. This method is compatible with a large variety of pyrroles and i...
Article
A study on C9‐imide acridinium photocatalysts with enhanced photoredox catalytic activity with respect to the well‐established C9‐mesityl acridinium salt is presented. The differences observed rely on the diverse accessibility of singlet charge‐transfer excited states, which have been proven by CASPT2/CASSCF calculations, fluorescence and quenching...