Mariola Tortosa

Mariola Tortosa
Universidad Autónoma de Madrid | UAM · Department of Organic Chemistry

PhD

About

64
Publications
2,515
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2,207
Citations
Citations since 2016
23 Research Items
1564 Citations
2016201720182019202020212022050100150200250
2016201720182019202020212022050100150200250
2016201720182019202020212022050100150200250
2016201720182019202020212022050100150200250
Introduction

Publications

Publications (64)
Article
Selective functionalization of the C-B bond in 1,2-bis(boronate) esters has emerged as a powerful tool to prepare 1,2-difunctionalized compounds with stereocontrol. Selective Suzuki cross-coupling, oxidation, amination, and homologation reactions serve as platforms to prepare a wide variety of compounds from a common intermediate. The exquisite sel...
Article
Full-text available
We present a strategy for the synthesis of spirocyclic cyclobutanes with modulable exit vectors based on the regioselective monoborylation of spirocyclobutenes. Using an inexpensive copper salt and a commercially available bidentate phosphine, a broad variety of borylated spirocycles have been prepared with complete regiocontrol. The boryl moiety p...
Article
Spirocyclobutenes provide a platform for the preparation of chiral spirocycles, through the diastereo- and enantioselective diboration of the double bond. Selective manipulation of the boryl moieties in the products allows unique control on the directionality and nature of the substituents on the spirocycle framework. Abstract The diastereo- and e...
Article
The diastereo‐ and enantioselective diboration of spirocyclobutenes provides a platform for the rapid preparation of a wide variety of chiral spirocyclic building blocks. The chemoselective functionalization of the carbon‐boron bond in the products, including a stereospecific sp3‐sp2 Suzuki–Miyaura cross‐coupling reaction, provides a powerful tool...
Article
Full-text available
Herein we describe the reactivity found between vinyl epoxides and catalytically generated copper-boryl complexes. By tuning the substituents of the alkene and/or the reaction conditions, 1,4-diols, allylic alcohols or cyclopropylboronates can be prepared. The stereochemical information of the vinyl epoxide is transferred to the products with high...
Chapter
Boronic acids and derivatives are highly versatile intermediates in synthetic chemistry. The development of modern borylation reactions has contributed to the emergence of boronic acid derivatives as a popular class of reagents. In recent years, catalytic borylation reactions have gained significant attention due to their efficiency, selectivity, a...
Article
We present an efficient strategy for the formal 1,4-reduction of vinyl epoxides that does not require superstoichiometric amounts of a strong reductant. Using a readily available copper catalyst and a diboron compound, a wide variety of enantioenriched allylic alcohols has been prepared. Additionally, epoxyenynes have been reduced in a 1,4-manner t...
Article
GABAA receptors (GABAARs) are targets for important classes of clinical agents (e.g., anxiolytics, anticonvulsants, and general anesthetics) that act as positive allosteric modulators (PAMs). Previously, using photoreactive analogs of etomidate ([3H]azietomidate) and mephobarbital [[3H]1-methyl-5-allyl-5-(m-trifluoromethyl-diazirynylphenyl)barbitur...
Article
α-Amidoboronic acids have received significant attention in recent years following the development of Bortezomib as an FDA-approved treatment of multiple myeloma and mantle cell lymphoma. More versatile methods to access α-amidoboronic acids continue to be developed. A direct method to access the precursors, α-amidoboronate esters, by iridium-catal...
Article
Strained boronate complexes have now been shown to enable an unprecedented cross-coupling reaction across a C–C σ-bond. Using this approach, highly functionalized cyclobutanes can be prepared with excellent stereocontrol from readily available reagents.
Article
Herein, we report a catalytic and stereospecific method for the preparation of enantioenriched α‐hydroxy cyclopropylboronates with control in four contiguous stereocenters. The reaction involves the borylation of readily available allylic epoxides using an inexpensive Cu(I) salt and a commercially available phosphine ligand. High diastereocontrol i...
Article
Herein, we report a catalytic and stereospecific method for the preparation of enantioenriched α‐hydroxy cyclopropylboronates with control in four contiguous stereocenters. The reaction involves the borylation of readily available allylic epoxides using an inexpensive Cu(I) salt and a commercially available phosphine ligand. High diastereocontrol i...
Article
Herein we describe a robust and practical method to prepare enantiomerically enriched trisubstituted allenes using alkyl Grignard reagents and bench stable propargylic ammonium salts. Excellent yields as well as regio-...
Article
Chiral cyclopropyl- and cyclobutylboronic esters and -silanes have become attractive intermediates for the preparation of functionalized small rings. This review highlights the stereoselective methods developed for their preparation, including both diastereo- and enantio­selective approaches. 1 Introduction 2 Stereoselective Synthesis of Cyclopropy...
Article
In this report, the enantioselective, copper-catalyzed borylation of β-amidoacrylates is disclosed. A broad variety of biologically important α-aminoboronates has been prepared with consistently high levels of enantiocontrol using an inexpensive copper catalyst and a commercially available chiral ligand. The method can be applied to the synthesis o...
Article
Chiral -allenols are prepared with high diastereocontrol through an unprecedented and spontaneous -oxygen elimination of an -epoxy vinyl boronate. Stochiometric experiments and DFT calculations support a dual role of the copper catalyst, which orchestrates the hydroboration and the syn-elimination step.
Article
We have developed a substitution reaction of propargylic ammonium salts with aryl Grignard reagents. The reaction is stereospecific, -regioselective and proceeds with exceptional functional group tolerance. Conveniently, a stable, inexpensive and commercially available copper salt is used and no added ligand is required.
Article
The first catalytic enantioselective synthesis of cyclobutylboronates, by using a chiral copper(I) complex, is reported. A broad variety of cyclobutanes have been prepared with consistently high levels of diastereo- and enantiocontrol. Moreover, this method constitutes the first report of an enantioselective desymmetrization of meso-cyclobutenes to...
Article
Full-text available
Glutamine and tyrosine-based amino acid conjugates of monocarboxylate transporter types 1 and 2 inhibitors (MCT1/2) were designed, synthesized and evaluated for their potency in blocking the proliferation of a human B lymphoma cell line that expresses the transporters Asct2, LAT1 and MCT1. Appropriate placement of an amino acid transporter recognit...
Article
The first catalytic enantioselective synthesis of cyclobutylboronates, by using a chiral copper(I) complex, is reported. A broad variety of cyclobutanes have been prepared with consistently high levels of diastereo- and enantiocontrol. Moreover, this method constitutes the first report of an enantioselective desymmetrization of meso-cyclobutenes to...
Article
In this report, we establish that DM-Segphos copper(I) complexes are efficient catalysts for the enantioselective borylation of para-quinone methides. This method provides straightforward access to chiral monobenzylic and dibenzylic boronic esters, with enantiomeric ratios up to 96:4, using a commercially available chiral phosphine. Standard manipu...
Article
Full-text available
An efficient and general copper(i)-catalyzed silylation of p-quinone-methides is described. Non-symmetric dibenzylic silanes are obtained in high yields under mild reaction conditions. These compounds can be used as bench-stable benzylic carbanion precursors.
Article
A new sheriff in town:­ para‐Quinone methides (p‐QMs) have been successfully used in asymmetric organocatalysis. Particularly, the asymmetric 1,6‐addition of phenyl malonate and different aldehydes to 2,6‐disubstituted p‐QMs has provided a rapid access to important chiral diarylmethines, highlighting the importance of these synthetic intermediates....
Article
The copper-catalyzed hydro- and carboboration of strained alkenes is presented. The reaction is highly diastereoselective and affords boronic ester derivatives many of which are difficult to synthesize by known methods. Competition experiments with different alkenes show that high levels of chemoselectivity can be achieved. Density functional theor...
Article
A novel Cu-catalyzed diastereo- and enantioselective desymmetrization of cyclopropenes to afford nonracemic cyclopropylboronates is described. Trapping the cyclopropylcopper intermediate with electrophilic amines allows for the synthesis of cyclopropylaminoboronic esters and demonstrates the potential of the approach for the synthesis of functional...
Article
Full-text available
Myc oncoproteins induce genes driving aerobic glycolysis, including lactate dehydrogenase-A that generates lactate. Here we report that Myc controls transcription of the lactate transporter SLC16A1/MCT1, and that elevated MCT1 levels are manifest in premalignant and neoplastic Eµ-Myc transgenic B cells and in human malignancies with MYC or MYCN inv...
Article
Boronic acid derivatives have become important intermediates in organic and medicinal chemistry and, as a result, the ­development of new methods that permit the efficient creation of C–B bonds under mild conditions has become an active field of research in organic synthesis. In the last ten years, copper-catalyzed borylation reactions have emerged...
Article
We describe the unexpected behavior of the arylsulfonylacetylenes, which suffer an "anti-Michael" addition of organolithiums producing their alkynylation under very mild conditions. The broad scope, excellent yields, and simplicity of the experimental procedure are the main features of this methodology. A rational explanation of all these results c...
Article
The first copper-catalyzed formal carboboration of alkynes, in which a C-B bond and a C-C bond are created in a single catalytic cycle, is presented. The reaction proceeds with high regioselectivity and syn-stereoselectivity to form tri- and tetrasubstituted vinylboronic esters from commercially available bis(pinacolato)diboron. A subsequent cross-...
Article
Chameleon: a new strategy for the synthesis of a wide variety of alkynyl derivatives by the reaction of substituted arylsulfonylacetylenes with organolithium species is described. The high yields, the simplicity of the experimental procedure, the broad scope of this reaction, and the formation of C(sp)-C(sp2) bonds without using transition metals a...
Article
Transition‐metal‐free alkynylation of Csp2 or Csp3 atoms in the reaction of sulfonylacetylenes with organolithium species is described by J. L. García Ruano, J. Alemán, et al. on page 8414 ff. Rather than the expected β‐attack, α‐attack of the nucleophiles occurs as a result of the chameleonic behavior of the sulfonyl group, which is able to coordi...
Article
Chamäleon: Eine neue Synthesestrategie für Alkinylderivate nutzt die Reaktion substituierter Arylsulfonylacetylene mit Organolithiumspezies (siehe Schema). Hohe Ausbeuten, eine große Substratbreite und der Verzicht auf Übergangsmetallverbindungen kennzeichnen diese leicht ausführbare CspC sp 2‐Verknüpfungsreaktion.
Article
Two sides of the same coin: Syn and anti 1,4-diols have been synthesized through the regio- and diastereoselective CuI-catalyzed boration of allylic epoxides (see scheme; pin=pinacolato, TES=triethylsilyl). In situ protection of the alcohol allows isolation of syn and anti 1,4- silyloxyboronates. Monoprotected 1,4-diols can be prepared by a one-pot...
Article
The discovery of nonproteinogenic amino acids among natural products, either in native state or as fragments of complex molecules, has increased the level of interest in this family of molecules from different scientific standpoints. Additionally, aside from the above considerations, the structural complexity of these molecules, having two vicinal...
Article
In this work, we report the design and synthesis of a set of fluorescent probes targeting the human 5-HT1A receptor (h5-HT1AR). Among the synthesized compounds, derivative 4 deserves special attention as being a high-affinity ligand (Ki = 2 nM) with good fluorescent properties (Iem > 1000 au and a fluorescence quantum yield, Φf, of 0.26), which ena...
Article
Sulfinyl dienynes undergo thermal and catalyzed IMDA cycloadditions, often at room temperature, to produce cyclohexa-1,4-dienes with good yields and high selectivities. Additionally, the products preserve a synthetically useful vinyl sulfoxide functionality. The selective manipulation of the double bonds in the cycloadducts has also been examined i...
Article
Highly diastereoselective Claisen rearrangements of acyclic allyl vinyl ethers bearing a chiral sulfoxide at C-5 provide gamma-delta-unsaturated aldehydes or ketones with up to two consecutive asymmetric centers in the molecule whilst preserving a useful vinyl sulfoxide. The reactivity of related vinyl sulfides and sulfones has also been examined i...
Article
The [2,3]-sigmatropic rearrangement of a variety of configurationally stable diastereomeric allylic sulfinyl dihydropyrans, produced by base-promoted cyclization of sulfinyl dienols, has been studied. In some cases, the efficient transformation of these substrates into dihydropyranols required an in-depth study of reaction conditions, with the pref...
Article
A convergent and highly stereocontrolled total synthesis of the cytotoxic macrolide (+)-superstolide A is described. Key features of this synthesis include the use of bimetallic linchpin 36b for uniting the C(1)-C(15) (43) and the C(20)-C(27) (38) fragments of the natural product, a late-stage Suzuki macrocyclization of 49, and a highly diastereose...
Article
The highly selective base-promoted cyclization of enantiopure sulfinyl dienols affords allylic sulfinyl dihydropyrans. The scope of this methodology, including the preparation of seven-membered rings, has been studied in depth. The reactivity of our sulfinyl dihydropyrans toward oxidation, imination, and dihydroxylation has been explored, and thus...
Article
A convergent and highly stereocontrolled synthesis of +-superstolide A (1) has been accomplished. Key steps of this synthesis include the intramolecular Suzuki reaction of 26 and the highly diastereoselective transannular Diels-Alder cyclization of macrocyclic octaene 3.
Article
The thio-Claisen rearrangement is a general and facile process that is often advantageous overthe standard Claisen rearrangement. Several asymmetric variants of the thio-Claisen rearrangement havebeen reported. The rearrangement of sulfonium salts and sulfoxides takes place even more readily. Alkenylsulfoxides and sulfilimines undergo a highly ster...
Article
Enantiopure 1-benzyl-2,3-disubstituted piperazines (4) have been synthesized by treatment of N-sulfinyl-N-benzyldiamino alcohols (1) with diethyl oxalate and sodium methoxide followed by reduction with borane. Alternatively, the sulfinamido group was preserved by an N-acylation/cyclization protocol using alpha-chloroacetyl chloride that led to the...
Article
Enantiopure hydroxy-2- and -3-sulfinyldienes undergo highly selective Diels-Alder cycloadditions with various dienophiles controlled by the chiral sulfur atom. The related hydroxy-2-sulfonyldienes display complementary pi-facial selectivity.
Article
2-Sulfinyl dienols undergo an efficient base-promoted cyclization to produce sulfinyl dihydropyrans with creation of two asymmetric centers. The configurational stability of the allylic sulfoxide in most cases is noteworthy. Simple manipulations lead to a variety of functionalized tetrahydropyrans.
Article
Readily available p-tolylsulfinimines undergo highly stereoselective [3 + 2] cycloadditions with azomethine ylides generated from α -iminoesters and LDA to produce N-sulfinylimidazolidines. In the presence of Lewis acids, p-tolylsulfinimines react with glycine iminoester enolates to produce N-sulfinylimidazolidines, after cyclization of open chain...
Article
The SN2′ displacement of readily available vinyl epoxy sulfoxides with organocopper reagents takes place in good yields with high anti selectivity and a good degree of E/Z stereocontrol to produce enantiopure α-hydroxy vinyl sulfoxides. A second allylic displacement on the related mesyloxy vinyl sulfoxides allows for the asymmetric construction of...
Article
[reaction: see text] The highly selective base-promoted cyclization of enantiopure sulfinyl dienols affords allylic sulfinyl dihydropyrans.
Article
The treatment of sulfinyl chlorohydrins with KO-t-Bu in THF generates epoxy vinyl sulfoxides that undergo an efficient base-induced rearrangement to generate enantiopure hydroxy 2-sulfinyl dienes. This novel process takes place with high chemo- and stereoselectivity. The chirality at sulfur effectively controls the geometry of the trisubstituted al...
Article
2-Sulfinyl butadienes tethered to unactivated alkynes undergo a facile thermal intramolecular Diels-Alder cycloaddition, often at room temperature, to produce cyclohexa-1,4-dienes with good selectivities, in high yields, and preserving the valuable vinyl sulfoxide functionality.
Article
A new procedure for the asymmetric synthesis of imidazolidines and vicinal diamines is reported. The 1,3-dipolar cycloaddition between nonracemic p-tolylsulfinimines and azomethine ylides generated in situ from alpha-iminoesters and LDA produces N-sulfinylimidazolidines with a high degree of stereocontrol. In contrast, the presence of Lewis acids p...
Article
The nucleophilic epoxidation of a variety of alpha'-(1-hydroxyalkyl) vinyl sulfones and sulfoxides has been studied. The sulfones give rise to anti oxiranes with modest (E) or excellent (Z) selectivities and in good yields. The (E)-sulfoxides display low reactivity within a reinforcing/nonreinforcing scenario. The use of t-BuOOLi in Et(2)O allows f...
Article
[reaction: see text] The highly selective Claisen rearrangements of substrates bearing a sulfinyl moiety at C-5 allow for creation of up to two asymmetric centers and preserve a useful vinyl sulfoxide.
Article
The treatment of enantiopure N-sulfinyl-N'-benzyldiaminoalcohols with diethyl oxalate and sodium methoxide followed by reduction with BH3 affords enantiopure 1-benzyl-2,3-disubstituted piperazines. A related sequence produces substituted monoketopiperazines in good yields.

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