Tomás Martín

Tomás Martín
Spanish National Research Council | CSIC · Molecular Science

Doctor of Philosophy

About

81
Publications
2,809
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2,182
Citations
Citations since 2017
9 Research Items
481 Citations
2017201820192020202120222023020406080
2017201820192020202120222023020406080
2017201820192020202120222023020406080
2017201820192020202120222023020406080
Introduction
Tomás Martín obtained his Ph.D. degree in 1996, at the University of La Laguna, Tenerife, Spain, working on the enantioselective synthesis of γ-lactones, under the guidance of Prof. Víctor S. Martín. He spent two years (1997-1998) at The Scripps Research Institute as a postdoctoral fellow, with Professor Julius Rebek working in supramolecular chemist. In 1999, he came back to Canary Islands, with a reincorporation contract of the Spanish MEC, joining the Victor S. Martín group. In 2002, he won a Ramón y Cajal contract. In 2005 he was promoted Tenured Scientist, and in 2018 Research Scientist at the Instituto de Productos Naturales y Agrobiología-CSIC, Spain. His research interests include supramolecular chemistry, organocatalysis and total synthesis of bioactive natural products.
Additional affiliations
August 2018 - present
Spanish National Research Council
Position
  • Researcher
July 2005 - July 2018
Spanish National Research Council
Position
  • Researcher
January 2002 - June 2005
Universidad de La Laguna
Position
  • Senior Researcher
Education
September 1991 - December 1996
Universidad de La Laguna
Field of study
  • Ciencias Químicas
September 1986 - June 1991
Universidad de La Laguna
Field of study
  • Ciencias Químicas

Publications

Publications (81)
Article
The heterogenization of homogeneous catalysts onto a solid support is a step towards a more sustainable chemistry. The recovery and reuse of catalysts is extremely important from a practical, economic and environmental point of view. In this regards, we report a series of polymer‐supported tetrahydropyran‐based hybrid dipeptides that serve as activ...
Article
Full-text available
Biomaterials-mediated bone formation in osteoporosis (OP) is challenging as it requires tissue growth promotion and adequate mineralization. Based on our previous findings, the development of scaffolds combining bone morphogenetic protein 2 (BMP-2) and matrix metalloproteinase 10 (MMP-10) shows promise for OP management. To test our hypothesis, sca...
Article
Full-text available
Cyclic products can be obtained through the intramolecular version of the Nicholas reaction, which requires having the nucleophile connected to the alkyne unit. Here, we report the synthesis of 1-oxa-3-cyclooctynes starting from commercially available (1R,3S)-camphoric acid. The strategy is based on the initial preparation of propargylic alcohols,...
Article
Two for one: Inverting the reactivity of the functional groups in ambiphilic molecules provides a new way to perform late‐stage enantiodivergence. Thus, starting from a common chiral substrate both enantiomers of the final product can be obtained. This concept is exemplified by the synthesis of substituted five‐ and six‐membered oxacycles. Abstrac...
Article
Inverting the reactivity of the functional groups in ambiphilic molecules provides a new synthetic strategy to carry out late‐stage enantiodivergence. Both enantiomers of the final compound can be obtained from a common chiral precursor. As a proof of concept, the synthesis of substituted five‐ and six‐membered oxacycles is described. The key step...
Article
Herein, we introduce and demonstrate how carbohydrates can be used as conformational control units of organocatalysts to tune their catalytic properties. New hybrid dipeptide‐like organocatalysts based on ζ‐sugar aminoacids and proline were prepared and tested for the asymmetric Michael addition of aldehydes to β‐nitrostyrenes. Taking full advantag...
Article
We report a new and efficient synthetic strategy that allows the access to flexible and functionalized benzocyclotrimers under mild conditions and in few steps. Negishi cross-coupling reaction was used for...
Article
A new series of hybrid dipeptide-like organocatalysts based on pyranoid ϵ- or ζ-amino acids and proline have been prepared for the asymmetric Michael addition of aldehydes to β-nitrostyrenes. The reaction proceeds under mild conditions to afford a wide range of γ-nitroaldehydes with up to 98% yield and up to 96% ee. These dipeptides are bifunctiona...
Article
The front cover picture, provided by Tomás Martín and co-workers illustrates a new type of organocatalyst based on sugar amino acids (SAA). These hybrid dipeptide-like organocatalysts combine two highly-modulable building blocks: amino acids and carbohydrates. The carbohydrate motif is embedded in the peptidic backbone and induces a well-defined co...
Article
The construction of coordination polymers based on flexible ligands in a pre-designed manner is a difficult task which needs deep knowledge of the ligands involved. With this objective in mind, we have investigated the complex formation between methanetriacetic acid (H3mta) and copper(ii) in the presence of 2,2′-bipyridine (bpy) as a blocking colig...
Article
Using a [2 + 2 + 2] cycloaddition/Mitsunobu reaction sequence, a convenient synthesis to access new benzocyclotrimer analogues has been developed. The new receptors have the geometry and functionality capable of recognizing the tetramethylammonium ion in the gas phase and in solution.
Article
Full-text available
Transition metal-free oxidations with air at room temperature have been achieved by simply using ascorbate (vitamin C) and catalytic amounts of menadione (vitamin K3). A combination of the mentioned vitamins transforms atmospheric oxygen into hydrogen peroxide, which is able to oxidize arylboronic acids and other chemical moieties.
Article
New pyranoid ε-sugar amino acids were designed as building blocks, in which the carboxylic acid and the amine groups were placed in positions C2 and C3 with respect to the tetrahydropyran oxygen atom. By using standard solution-phase coupling procedures, cyclic homooligomers containing pyranoid ε-sugar amino acids were synthesized. Conformation ana...
Article
The enantioselective formal synthesis of (-)-isolaurepinnacin and (+)-rogioloxepane A has been achieved. The key steps are an intermolecular Nicholas reaction with a β-hydroxy-γ-lactone as the nucleophile, to form branched linear ethers, and an olefin ring-closing metathesis to obtain the oxepene core.
Article
Ascorbic acid (vitamin C) has been used as a radical initiator in a metal-free direct CH arylation of (hetero)arenes. Starting from an aniline, the corresponding arenediazonium ion is generated in situ and immediately reduced by vitamin C to an aryl radical that undergoes a homolytic aromatic substitution with a (hetero)arene. Notably, neither hea...
Article
Three new metal-organic framework structures containing Eu(III) and the little explored methanetriacetate (C7H7O6(3-), mta(3-)) ligand have been synthesized. Gel synthesis yields a two-dimensional framework with the formula [Eu(mta)(H2O)3]n·2nH2O, (I), while two polymorphs of the three-dimensional framework material [Eu(mta)(H2O)]n·nH2O, (II) and (...
Article
This account describes our studies on the synthesis of natural products that contain cyclic ethers in their structures. An overview of the main methodologies is presented and several total syntheses developed by the group are described. We also discuss new applications based on the use of Prins and Nicolas reactions as key steps in the preparation...
Article
An expedient methodology to synthesize macrocyclic compounds in one step based on the Nicholas reaction is disclosed. The key step features two intermolecular reactions followed by an intramolecular reaction from the starting dicobalt hexacarbonyl-propargylic complex. The macrocycles obtained were modified through [2 + 2 + 2] cycloaddition, generat...
Article
Positive cooperativity between host conformational equilibria and guest binding has been widely reported in protein receptors. However, reported examples of this kind of cooperativity in synthetic hosts are scarce and largely serendipitous, among other things because it is hard to envision systems which display this kind of cooperativity. In order...
Article
Cooperativity is one of the most relevant features displayed by biomolecules. Thus, one of the challenges in the field of supramolecular chemistry is to understand the mechanisms underlying cooperative binding effects. Traditionally, cooperativity has been related to multivalent receptors, but Williams et al. have proposed a different interpretatio...
Article
Natural inspiration: Based on the biosynthesis of squalene-derived polyethers, a total synthesis of teurilene is described. The carbocation formation in the Nicholas reaction serves to control the initiation of a polyepoxide ring-opening cascade. The three furan rings present in teurilene were obtained in excellent yield in one step. Boc=tert-butox...
Article
Full-text available
Several, if not all adrenergic β-blockers (β-Bs), accumulate progressively inside secretory vesicles in a time-and concentration-dependent manner, and could be considered to be false neurotransmitters. This transmitter effect is most likely unrelated to their ability to block adrenergic receptors, but it could explain the delay in lowering arterial...
Article
Doppelter Einfluss: Nichtkovalente Wechselwirkungen in einem Rezeptor können zu einer enantioselektiven Gastbindung führen. Ein solcher kooperativer Effekt wird für ein einfaches synthetisches System beschrieben und quantifiziert, in dem eine Wasserstoffbrücke im Rezeptor mit einer CH-π-Wechselwirkung kooperiert, die ausschließlich mit dem D-Enanti...
Article
A novel halogenation reaction from sulfonates catalyzed by iron(III) is described. The reaction can be performed as a stoichiometric or a catalytic version. This reaction provides a convenient strategy for the efficient access to structurally diverse secondary chlorides, bromides and iodides. The stereochemical course of the reaction is governed by...
Article
This is a theoretical study carried out on the experimental data obtained for 90 binary systems comprised of alkyl esters with dibromoalkanes, using data from previous publications and those corresponding to 20 mixtures presented here. The experimental part of this work corresponds to experimental measurements of HmE and VmE at T = 298.15 K and atm...
Article
Full-text available
Herein we report the crystal structures of tubular self-assemblies of flexible macrooligolides. The assembly is driven by the propensity of the macrocycles to create nearly flat structures displaying a void space within them and the cooperativity of weak directional interactions such as dipole–dipole interactions and CHOhydrogen bonds and non-direc...
Article
A new approach to lauroxanes by a powerful and highly convergent methodology based on iterative use of Co(2)(CO)(6)-acetylenic complexes is described. The strategy employs an intermolecular Nicholas reaction to form unsaturated branched linear ethers, a ring closing metathesis to obtain the cobalt complex cyclic ethers, and an isomerization promote...
Article
The preparation, X-ray crystallography and magnetic investigation of the first examples of methanetriacetate (mta)-containing lanthanide(III) complexes of formulae [Gd(mta)(H(2)O)(3)](n)4 n H(2)O (1) [Gd(mta)(H(2)O)(3)](n)2 n H(2)O (2) and [Gd(2)(mta)(2)(H(2)O)(2)](n)2 n H(2)O (3) are described herein. This tripodal ligand promotes the formation of...
Article
Good things come in small interactions: The high chiral discrimination displayed by a new receptor with ammonium salts of aromatic a-amino acid methyl esters is mainly the result of one of the weakest noncovalent interactions, the CH-π interaction (see picture). The interaction has been identified and quantified, and its contribution to the chiral...
Article
A new and efficient methodology to prepare α,α'-disubstituted linear ethers through an intermolecular Nicholas reaction (interNR) is described. cis-2,8-Disubstituted oxocanes, cis-2,9-disubstituted oxonanes, their trans isomers, and their parent unsaturated precursors were prepared from the corresponding Co2(CO)6-cycloalkynic ethers. Key steps in s...
Article
Linear diterpenes isolated from aerial parts of Baccharis thymifolia (1-3) were tested for insect growth inhibitory activity against Tenebrio molitor larvae. Compounds 4-16 were prepared by various chemical transformations. The diterpenes 6,10-(E,E)-thymifodioic acid (1), the butenolide 3, and the derivatives 4,11, and 14 produced developmental def...
Article
A new, practical, and mild procedure for the selective cleavage of a tert-butoxycarbonyl group (Boc) in N-Boc-N-acyl-diprotected amines is described. When applied to α-amino acids, complete integrity of the stereochemistry was observed. The use of N,N-di-Boc-α-amino-δ- and γ-hydroxy esters provided both δ- and γ-lactones in very good yields. The me...
Article
In this study, we synthesized a series of enantiomerically pure (2R,3R)- and (2R,3S)-disubstituted tetrahydropyrans bearing a CH2O spacer group on the side chain at position 2 of the heterocyclic ring. The in vitro antiproliferative activities of the compounds were examined in the human solid tumor cell lines A2780 (ovarian cancer), SW1573 (non-sma...
Article
Samarium(II) iodide promotes the stereoselective synthesis of cis-beta-alkoxy-gamma-alkyl-gamma-lactones under mild conditions starting from linear precursors. The in vitro antiproliferative activities were examined in the human solid tumor cell lines from diverse origin A2780, SW1573, and WiDr. From the growth inhibition data a structure-activity...
Article
In this study, we synthesized a series of enantiomerically pure (2R,3R)-disubstituted tetrahydropyrans with diverse functional groups. The in vitro antiproliferative activities were examined in the human solid tumor cell lines A2780 (ovarian cancer), SW1573 (non-small cell lung cancer), and WiDr (colon cancer). Overall, the results show the relevan...
Article
A short and efficient enantiomeric synthesis of fused tetrahydrofuran derivatives is reported. The methodology is based on a regio- and stereoselective double exo-cyclization of enantiomeric bis-epoxy-diols. The six stereocenters of the bis-epoxy diols were introduced by the application of Katsuki–Sharpless asymmetric epoxidation and Sharpless asym...
Article
The concept of molecular simplification as a drug design strategy to shorten synthetic routes, while keeping or enhancing the biological activity of the lead drug, has been applied to (+)-muconin, an acetogenin with remarkable cytotoxicity. A novel approach that enables the stereoselective synthesis of such a natural compound or its enantiomer from...
Article
Cis-2,8-disubstituted oxocanes and the parent unsaturated precursors were prepared from the corresponding Co2(CO)6-cycloalkynic ethers. Key steps in such synthesis were the ether linkage formation by intermolecular Nicholas reaction, RCM of the suitable acyclic dienyl ether and montmorillonite K-10 induced isomerization of the complexed cycloalkyne...
Article
Enantiomerically pure (2R,3S)-disubstituted tetrahydropyrans with diverse functional groups were synthesized. These derivatives were used as a model to study the influence of the tert-butyl dimethyl silyl group in the anticancer activity. The in vitro cytotoxicity was evaluated against a panel of six human cancer cells from diverse origin (MCF7, T-...
Article
[reaction: see text] A simple and convenient one-pot protocol for the chemoselective C2-homologation of carbohydrate-derived glycols is described. The method comprises the chemoselective oxidation of the glycol to the corresponding hydroxyaldehyde and the subsequent Wittig alkenylation. In addition, the method does not need selective protective gro...
Article
Full-text available
In this study, we synthesized a series of enantiomerically pure (2R,3S)-disubstituted tetrahydropyranes with diverse functional groups using known methodologies. In addition to the tert-butyl dimethyl silyl group, other common protecting groups for hydroxyl groups such as allyl, acetate, and benzoate were used to obtain appropriate derivatives. Pur...
Article
The cis-2-alkyl-3-oxy-tetrahydropyran unit as a novel structure for the design and synthesis of a new type of ionophores with C2-symmetry is reported. The synthesis of seven different macrolides and a crown ether and their cation complexation properties were investigated. The X-ray crystal structure of some of the receptors provides valuable inform...
Article
The use of Montmorillonite K-10 as a convenient acid component in the Nicholas reaction is described. Its use permits functional selectivity, inter- and intramolecular reactions and convenience in the experimental conditions. A four-step one-pot [Co2(CO)6–acetylene complex formation, THP-removal, cyclization and complex cleavage] process permits th...
Article
Full-text available
The proteasome is a new interesting target in cancer drug therapy and the protea- some-inhibitor bortezomib has shown effect in myeloma patients. It is of interest to quickly find and evaluate new substances with proteasome-inhibiting activity. We have developed a rapid method for the identification of compounds with protea- some-inhibiting activit...
Article
The use of cis-2-alkyl-3-oxy-tetrahydropyran unit is reported as a novel structure for the design and synthesis of a new type of ionophore with C2-symmetry. The synthesis of five macrolides and their complexation properties were investigated. The template effect as an effective tool to improve the selectivity and yield in the macrolactonization pro...
Article
[reaction: see text] The intramolecular nucleophilic attack of the epoxides on the exo-Co(2)(CO)(6)-propargylic cations provided cyclic ethers in good yields. The use of substrates with stereochemically defined oxiranes provided polysubstituted tetrahydropyrans and oxepanes with a high degree of stereocontrol. The cyclization is sensitive to the na...
Article
Full-text available
Four complementary hydrogen bonds between sulfamides and ureas link adjacent hydrogen-bonded ribbons to form sheets in the solid-state; this interaction is investigated in solution using model urea and sulfamide compounds.
Article
The intramolecular attack of a hydroxy group on an exo-biscobalthexacarbonyl propargylic cation provides cyclic ethers with six- to nine-membered rings. The scope and limitations of the methodology are described. The reaction is stereoselective when additional stereocenters are present, providing iterative methodology to access ladder-like cyclic e...
Article
An efficient synthesis of the title compounds as pure enantiomers is reported. The method is based on the intramolecular trapping of a carbocation generated by acid treatment of exo-Co2(CO)6-propargyl alcohols by a stereochemically controlled secondary hydroxy group located in a suitable chain.
Article
[reaction: see text]. The trapping of cations generated from Co2(CO)6-bispropargylic alcohols provided diethers in good yield. The procedure is also valid when two vicinal acetylenes are present. The methodology can be applied to the synthesis of symmetrical or unsymmetrical linear or cyclic propargylic ethers. The use of substrates with a stereoch...
Article
Studies on the different congeners of the softball were undertaken to explore structural variants for enantioselective encapsulation. Two different spacer elements in the monomeric subunit render the dimeric softball chiral although the monomer itself is achiral. The dimers represent capsules with dissymmetric cavities with volumes ranging from 190...
Article
The enantioselective synthesis of trans-(+)-laurediol, (2S,3S,5R)-5-[(1R)-1-hydroxy-9-decenyl]-2-pentyltetrahydro-3-furanol, and (2S,3S,5S)-5-[(1S)-1-hydroxy-9-decenyl]-2-pentyltetrahydro-3-furanol are described. In addition, a formal synthesis of trans-(-)-kumausyne is also developed. All the synthetic procedures have in common the use of enantiom...
Article
Herein we report the synthesis of a molecule that self-organizes through hydrogen bonds into discrete tetrameric capsular species, encapsulating large polycyclic guest molecules. The unique folded structure of the assembled state is determined by correlation spectroscopy in conjunction with molecular modeling. Pendant methoxyl groups are essential...
Article
Achiral building blocks form nonracemic, chiral capsular hosts with enantioselective molecular recognition properties. The chirality is imprinted by a chiral guest template, and persists for hours in organic solvents after the guest has been removed. The exchange equilibria are depicted, with the guest exchanges shown by the horizontal equilibria a...
Article
A highly convergent and short synthesis of trans-(+)-laurediol is presented. The synthesis features a highly efficient construction of a cis-3-hydroxy-γ-butyrolactone through a Sharpless AD reaction of a β,γ-unsaturated ester.
Article
A nonracemic compound is synthesized and shown to assemble reversibly through hydrogen bonding to form a cyclic tetramer. The chiral arrangement of atoms in the individual pieces becomes amplified through self-assembly to yield multiple functional groups asymmetrically arranged within the cavity. The tetrameric capsule shows a special affinity for...
Article
Full-text available
Encapsulation complexes are reversibly formed assemblies in which small molecule guests are completely surrounded by large molecule hosts. The assemblies are held together by weak intermolecular forces and are dynamic: they form and dissipate on time scales ranging from milliseconds to days-long enough for many interactions, even reactions, to take...
Article
Reversibly self-assembling host–guest complexes of the softball type are characterized by electrospray ionization mass spectrometry. Quaternary ammonium ions serve simultaneously as guests and ion labels. Isotope pattern analysis, inclusion of labeled guests, heterodimer experiments, size and shape dependence, and collision-induced fragmentation re...
Article
The interaction of quaternary ammonium ion guests with self-assembling hosts was examined by 1H NMR and ESI-MS experiments. The hosts consist of four identical, self-complementary subunits, reversibly joined in a capsular assembly through hydrogen bonding. Both approaches show the ammonium ions to be encapsulated, held within the hollow shell of th...
Article
Multiple copies of a molecule, held together in finite aggregates, give rise to properties and functions that are unique to their assembled states. Because these aggregates are held together by weak forces operating over short distances, a premium is placed on complementarity: The molecular surfaces must facilitate specific interactions that direct...
Article
The enantiospecific synthesis of unnatural unsaturated and saturated α-amino acids based on a Wittig type reaction is described. The versatile synthetic intermediates, l-glutamic and l-aspartic acid semialdehydes, are obtained from the corresponding N,N-di-Boc-diesters, by the selective reduction of the ω-ester with DIBAL® under controlled conditio...
Article
Here we report on a simple, efficient, and general method to prepare unsaturated alpha-amino fatty acids in their enantiomeric forms, which eventually can be transformed into the saturated products by simple hydrogenation.
Article
Full-text available
Molecules with self-complementary surfaces interact through weak intermolecular forces to form assemblies, and the assembled states frequently exhibit distinctive properties. Described here are systems in which symmetrical molecules assemble through hydrogen bonding to produce capsules with dissymmetric cavities. The capsules form and dissipate on...
Article
The synthesis of isoavenaciolide and avenaciolide in their natural enantiomeric forms are described. In both syntheses, α-(phenylthio)-β-[(methoxycarbonyl)methyl]-γ-lactones obtained by the base-induced cyclization of enantiomerically enriched γ-[(phenylthio)acyl] α,β-unsaturated esters were used as starting materials. In the isoavenaciolide synthe...
Article
The intramolecular Michael addition of enantiomerically enriched γ-[(phenylthio)acyl]oxy, β-unsaturated esters opens a way to the synthesis of saturated γ-lactones, α-methylene butyrolactones and butenolides of high enantiomerical purity. The method is complemented by the alkylation of the obtained α-benzenesulfonyl-γ-lactones which with an unusual...
Article
Enantiomerically enriched (+)-grandisol and (+)-fraganol were synthesized using as the key step a new stereoselective synthesis of cyclobutanes fused to γ-lactones by a stereochemically-controlled intramolecular alkylation of α-benzenesulfonyl-γ-lactones. This method provides a way to synthesize the enantiomers in a straightforward manner.
Article
The synthesis of polysubstituted gamma-lactones by the base-induced cyclization of enantiomerically enriched gamma-((phenylthio)acyl)oxy alpha,beta-unsaturated esters obtained from 2,3-epoxy alcohols is described. The procedure is highly stereoselective and compatible with a wide range of functionalities (ester, tetrahydropyranyl ether, silyl ether...
Article
The oxidation of alpha-(phenylthio) gamma-lactones obtained by the base-induced cyclization of enantiomerically enriched gamma-[(phenylthio) acyl]-alpha,beta-unsaturated esters to sulfones in those cases where the a-carbon has an available proton and further basic alkylation led to an unexpected facial selectivity. The reaction proceeded smoothly w...

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