Catalytic enantioselective Friedel–Crafts alkylation at the 2-position of indole with simple enones

Abstract A procedure for the enantioselective alkylation of indole at the 2-position with simple non-chelating enones is described for the first time. Reaction between 4,7-dihydroindole and enones in the presence of zirconium(IV)–BINOL complexes, followed by a p -benzoquinone oxidation gives indoles alkylated at the 2-position with good yields and moderate enantioselectivities.

Nucleophilic benzoylation using lithiated methyl mandelate as a synthetic equivalent of the benzoyl carbanion. Oxidative decarboxylation of α-hydroxyacids

Abstract The synthesis of alkyl aryl ketones using lithiated methyl mandelate as a synthetic equivalent of the benzoyl carbanion is reported (Umpolung). The methodology involves alkylation of methyl mandelate, hydrolysis of the ester group and oxidative decarboxylation of the resulting α-hydroxyacids. The last step is carried out in a catalytic aerobic way using a Co(III) complex in the presence of pivalaldehyde under very mild and advantageous conditions. The procedure is also applied to methyl mandelates substituted on the aromatic ring.

ChemInform Abstract: Synthesis of Functionalized Indoles with a Trifluoromethyl-Substituted Stereogenic Tertiary Carbon Atom Through an Enantioselective Friedel-Crafts Alkylation with β-Trifluoromethyl-α,β-enones.

Chiral complexes of BINOL-based ligands with zirconium tert-butoxide catalyze the Friedel-Crafts alkylation reaction of indoles with beta-trifluoromethyl-alpha,beta-unsaturated ketones to give functionalized indoles with an asymmetric tertiary carbon center attached to a trifluoromethyl group. The reaction can be applied to a large number of substituted alpha-trifluoromethyl enones and substituted indoles. The expected products were obtained with good yields and ees of up to 99%.

Organocatalytic enantioselective Strecker reaction with seven-membered cyclic imines

[EN] A highly enantioselective Strecker reaction with dibenzo[b,f][1,4]oxazepines has been described using a dihydroquinine-derived thiourea as organocatalyst. The reaction affords chiral 10,11-dihydrodibenzo[b,f][1,4] oxazepine 11-carbonitrile derivatives in excellent yields (up to 99%) and excellent enantioselectivities (up to 98%) under mild reaction conditions.

Highly Diastereoselective Arylation of (S)-Mandelic Acid Enolate: Enantioselective Synthesis of Substituted (R)-3-Hydroxy-3-phenyloxindoles and (R)-Benzylic Acids and Synthesis of Nitrobenzophenones.

An easy access to substituted (R)-3-hydroxy-3-phenyloxindoles, (R)-benzylic acids, and benzophenones is described. The reaction of the lithium enolate of the (2S,5S)-cis-1,3-dioxolan-4-one derived from optically active (S)-mandelic acid and pivalaldehyde with several o- and p-halonitrobenzenes proceeds readily to give the corresponding arylation products in good yields and diastereoselectivities. The reduction of the nitro group with Zn/HCl/EtOH in the o-nitro arylation products with concomitant intramolecular aminolysis of the dioxolanone moiety leads directly to enantiomerically pure (R)-3-hydroxy-3-phenyloxindoles. On the other hand the basic hydrolysis of the dioxolanone moiety in all t…

Ferromagnetic Coupling through Spin Polarization in a Dinuclear Copper(II) Metallacyclophane.

[DT] Von organischen Radikalen zu Metallkomplexen konnte das bekannte Konzept für Ferroelektrika erfolgreich ausgedehnt werden: Die Abbildung zeigt ein Cyclophan-artiges Molekül mit einem Triplett-Grundzustand, in dem zwei CuII-Zentren von einem doppelten m-Phenylendiamid-Gerüst zusammengehalten werden.

NMR Spectroscopic Characterization and DFT Calculations of Zirconium(IV)-3,3′-Br2–BINOLate and Related Complexes Used in an Enantioselective Friedel–Crafts Alkylation of Indoles with α,β-Unsaturated Ketones

Experimental and theoretical studies on the structure of several complexes based on (R)-3,3'-Br-2-BINOL ligand and group (IV) metals used as catalysts in an enantioselective Friedel-Crafts alkylation of indoles with alpha,beta-unsaturated ketones have been carried out. NMR spectroscopic studies of these catalysts have been performed, which suggested that at room temperature the catalysts would form a monomeric structure in the case of Ti-IV and a dimeric structure in the cases of Zr-IV and Hf-IV. Density functional theory (DFT) calculations clearly corroborate the conclusions of these experimental spectroscopic studies. The dimeric structure with a doubly bridged motif [Zr-2(IV)(mu-(R)-3,3'…

Sheets of alternating chirality in the structure of a novel iron(III) complex with a cyclic oxamide ligand

An organic–metalloorganic analogue of the inorganic clay minerals has been obtained from the cyclization of N,N′-bis(ethoxalyl)phenylenediamine in basic medium in the presence of iron(III) ions leading to formation of a cyclic oxamide ligand (L). The combination of intramolecular (covalent) interactions between metal and ligand and intermolecular (noncovalent) ionic interactions creates a novel layered compound with an intriguing crystal structure (shown on the right).

Highly enantioselective copper(I)-catalyzed conjugate addition of terminal alkynes to 1,1-difluoro-1-(phenylsulfonyl)-3-en-2-ones: new ester/amide surrogates in asymmetric catalysis.

A highly enantioselective copper-catalyzed conjugate alkynylation of monoactivated enones, namely 1,1-difluoro-1-(phenylsulfonyl)-3-en-2-ones, is described. The reaction products are obtained with good yields and excellent enantioselectivities (from 92 to 99% ee). The β-alkynylated difluoro(phenylsulfonyl) ketones can be converted into the corresponding β-alkynylated difluoro- and trifluoromethyl ketones, esters and amides. This is the first example on the use of 1,1-difluoro-1-(phenylsulfonyl)-3-en-2-ones as substrates in an enantioselective reaction, which have been shown to be new ester/amide surrogates.

Body Image Perception in Mexican University Athletes VS Non-Athletes

The objective of this study consisted in determining the differences and similarities among Mexican University students who practice a sport on a regular basis with those who do not do, concerning their body image perception to their actual, ideal, social and body size dissatisfaction. A total sample of 304 male University students, aged 18-29 years participated in this study; 146 of them practice a sport and participate regularly in a tournament or competition. A quantitative approach with a descriptive and transversal survey design was used. All the participants completed the Contour Drawing Rating Scale adapted and computerized by [1]. The results of the one-way multivariate analysis of …

Synthesis of Functionalized Indoles with a Trifluoromethy-Substituted Stereogenic Tertiary Carbon Atom Through an Enantioselective Friedel-Crafts Alkylation with beta-Trifluoromethyl-alpha, beta-enones

[EN] Chiral complexes of BINOL-based ligands with zirconium tert-butoxide catalyze the Friedel-Crafts alkylation reaction of indoles with beta-trifluoromethyl-alpha,beta-unsaturated ketones to give functionalized indoles with an asymmetric tertiary carbon center attached to a trifluoromethyl group. The reaction can be applied to a large number of substituted alpha-trifluoromethyl enones and substituted indoles. The expected products were obtained with good yields and ees of up to 99%.

ChemInform Abstract: Organocatalytic Asymmetric Addition of Naphthols and Electron-Rich Phenols to Isatin-Derived Ketimines: Highly Enantioselective Construction of Tetrasubstituted Stereocenters.

A quinine-derived thiourea organocatalyst promoted the highly enantioselective addition of naphthols and activated phenols to ketimines derived from isatins. The reaction afforded chiral 3-amino-2-oxindoles with a quaternary stereocenter in high yields (up to 99 %) with excellent enantioselectivity (up to 99 % ee). To the best of our knowledge, this transformation is the first highly enantioselective addition of naphthols to ketimines.

Catalytic enantioselective addition of terminal alkynes to aromatic aldehydes using zinc-hydroxyamide complexes

[EN] A mandelamide ligand, derived from (S)-mandelic acid and (S)-phenylethanamine, catalyzes the addition of aryl-, alkyl-and silyl-alkynylzinc reagents to aromatic and heteroaromatic aldehydes with good yields and good to high enantioselectivities.

Technology as 'Applied Science': a Serious Misconception that Reinforces Distorted and Impoverished Views of Science

The current consideration of technology as "applied science", this is to say, as something that comes "after" science, justifies the lack of attention paid to technology in science education. In our paper we question this simplistic view of the science-tecnology relationship, historically rooted in the unequal appreciation of intellectual and manual work, and we try to show how the absense of the technological dimension in science education contributes to a naive and distorted view of science which deeply affects the necessary scientific and technological literacy of all citizens. Fil: Gil Perez, Daniel. Universidad de Valencia; España Fil: Vilches, Amparo. Universidad de Valencia; España F…

Enantioselective Addition of Dimethylzinc to Aldehydes Catalyzed by N-Substituted Mandelamide-Ti(IV) Complexes.

Abstract Amides derived from ( S )-(+)-mandelic acid in the presence of titanium isopropoxide catalyze the enantioselective addition of dimethylzinc to aromatic aldehydes with good yields and ee up to 90%.

Chemistry and reactivity of mononuclear manganese oxamate complexes: Oxidative carbon-carbon bond cleavage of vic-diols by dioxygen and aldehydes catalyzed by a trans-dipyridine manganese(III) complex with a tetradentate o-phenylenedioxamate ligand

[EN] Two new mononuclear octahedral manganese(III) complexes with the tetradentate equatorial ligand o-phenylenebis(oxamate) (opba) and two aquo (1a) or two pyridine (1b) axial ligands have been synthesized and characterized structurally, magnetically, and electrochemically. The cyclovoltammogram of 1a in acetonitrile (25 degrees C, 0.1 M Bu4NPF6) shows an irreversible one-electron oxidation peak at a high anodic potential (E-ap = 1.03 V versus SCE), while that of 1b shows two well-separated one-electron oxidation peaks at moderate to high anodic potentials (E-ap = 0.92 and 1.27 V versus SCE), the first redox-wave being quasireversible in nature. The access to formally high-valent Mn-IV and…

Valores personales en el baloncesto de formación y su relación con el bienestar y la intención futura de práctica a través de la motivación

Tomando como marco teórico la teoría de los valores humanos (Schwartz, 1992; Schwartz et al., 2012), y la teoría de la autodeterminación (Deci y Ryan, 1985, 2000), el objetivo del estudio consistió en poner a prueba un modelo, en una muestra de 115 jugadores jóvenes de baloncesto ( M edad = 13.98, DT = 0.13), en el que se hipotetizó que los diferentes tipos de motivación (motivación autónoma, controlada y no motivación) actuarían como mediadores de la relación entre los va lores informados por los jugadores (auto - trascendencia, conservación, auto - promoción y apertura al cambio) y los indicadores de bienestar (vitalidad subjetiva y afectos positivos), así como con la intención futura de …

ChemInform Abstract: Enantioselective Zirconium-Catalyzed Friedel-Crafts Alkylation of Pyrrole with Trifluoromethyl Ketones.

The first catalytic enantioselective Friedel−Crafts alkylation of pyrrole with 2,2,2-trifluoroacetophenones to give pyrroles with a trifluoromethyl-substituted tertiary alcohol moiety bearing a quaternary stereogenic center is described. The reaction is achieved in the presence of a 3,3′-dibromo-BINOL-Zr(IV) complex to give the expected products with high yields (up to 98%) and good enantioselectivities (up to 93% ee). The absolute stereochemistry of the products has been determined by chemical correlation.

Validation of the Spanish version of multidimensional inventory of perfectionism in young athletes

espanolEl InventarioMultidimensional de Perfeccionismo en Deporte (MIPS) es una medida deportiva especifica del perfeccionismo desarrollado a partir de una combinacion de diferentes modelos multidimensionales. Este estudio analiza las propiedades psicometricas del MIPS en una muestra espanola de jovenes futbolistas. Participaron 429 futbolistas espanoles con edades comprendidas entre 9 y 13 anos. Los analisis factoriales confirmatorios mostraron que un modelo bidimensional obtenia adecuados indices de ajuste y los coeficientes alfa de Cronbach mostraron niveles de fiabilidad interna aceptables. La validez criterial y convergente del MIPS espanol estudiada con adolescentes futbolistas ha sid…

Diastereoselective Michael addition of (S)-mandelic acid enolate to 2-arylidene-1,3-diketones: enantioselective diversity-oriented synthesis of densely substituted pyrazoles

[EN] A diversity-oriented approach to enantiomerically pure densely substituted pyrazoles, ¿-aryl-¿-pyrazolylatrolactic acid and ¿-aryl-¿-pyrazolylacetophenones has been developed. The approach utilises the conjugated addition of the lithium enolate of the (2S,5S)-cis-1,3-dioxolan-4-one derived from optically active (S)-mandelic acid and pivalaldehyde to several 2-arylidene-1,3-diketones, which proceeds readily to give the corresponding Michael adducts in good yields and diastereoselectivities. The cyclocondensation of the 1,3-diketone moieties present in Michael adducts with several hydrazines leads to enantiomerically pure densely substituted pyrazoles. Subsequent basic hydrolysis of the …

ChemInform Abstract: Enantioselective Synthesis of Substituted Indoles Through Zirconium(IV)-Catalyzed Friedel-Crafts Alkylation.

The method allows the introduction of a C-3 side chain bearing a tertiary stereogenic center.

Enantioselective Synthesis of Substituted Indoles Through Zirconium(IV)-Catalyzed Friedel–Crafts Alkylation

The chiral complex of ( R )-3,3′-Br 2 -BINOL and zirconium tert -butoxide catalyzes the Friedel–Crafts alkylation of indoles with enones bearing an alkyl or fluorinated group at the β-position to give indoles having a side chain at the C3 position with a tertiary stereogenic center in good yields and with excellent enantioselectivities.

ChemInform Abstract: Catalytic Enantioselective Friedel—Crafts Alkylation at the 2-Position of Indole with Simple Enones.

Abstract A procedure for the enantioselective alkylation of indole at the 2-position with simple non-chelating enones is described for the first time. Reaction between 4,7-dihydroindole and enones in the presence of zirconium(IV)–BINOL complexes, followed by a p -benzoquinone oxidation gives indoles alkylated at the 2-position with good yields and moderate enantioselectivities.

Manganese(iv) oxamato-catalyzed oxidation of secondary alcohols to ketones by dioxygen and pivalaldehyde

A new manganese(IV) oxamato complex possessing a bis(moxo) dimanganese core has been synthesized, magnetically and structurally characterized, and found to catalyze the aerobic oxidation of secondary alcohols to ketones with cooxidation of pivalaldehyde to pivalic acid with good yields and high selectivities. Ruiz Garcia, Rafael, Rafael.Ruiz@uv.es ; Fernandez Picot, Isabel, Isabel.Fernandez@uv.es ; Pedro Llinares, Jose Ramon, Jose.R.Pedro@uv.es ; Rosello Arce, Antonio Luis, Antonio.L.Rosello@uv.es ; Castro Bleda, Isabel, Isabel.Castro@uv.es

Enantioselective Friedel-Crafts Alkylation of Indoles with (E)-1-Aryl-4-benzyloxybut-2-en-1-ones Catalyzed by an (R)-3,3′-Br2BINOLate-Hafnium(IV) Complex

A highly enantioselective Friedel–Crafts reaction of unprotected indoles with (E)-1-aryl-4-benzyloxybut-2-en-1-ones catalyzed by a new chiral [Hf{(R)-3,3′-Br2-BINOL}(OtBu)2]2 complex has been developed to functionalize the C-3 position of the indole nucleus with a side chain bearing a 1,4-difunctionalized moiety and a benzylic stereogenic center. The reaction proceeds in good to excellent yields and excellent enantioselectivities (up to 97 % ee). The usefulness of this approach was illustrated with the synthesis of a tryptophol derivative.

Aerobic epoxidation of olefins catalysed by square-planar cobalt(III) complexes of bis-N,N′-disubstituted oxamides and related ligands

The new square-planar nickel(II) complexes of o-phenylenebis(N′-methyloxamidate) and related ligands catalyse the aerobic epoxidation of olefins with co-oxidation of pivalaldehyde; the modulation of catalytic activity by substituents along this series of metal complexes points out the role of high-valent nicke(IV)-oxo species as the putative intermediate in these oxygen atom transfer reactions.

Two guaianolides from Centaurea collina

Abstract Two guaianolides isolated from the aerial parts of Centaurea collina were identified as 3β-hydroxy-8α-epoxymethylacriloiloxy-4(15),10(14),11(13 and its 11β,13-dihydro derivative by spectroscopic methods.

ChemInform Abstract: Catalytic Enantioselective Addition of Terminal Alkynes to Aromatic Aldehydes Using Zinc-Hydroxyamide Complexes.

A mandelamide ligand, derived from (S)-mandelic acid and (S)-phenylethanamine, catalyzes the addition of aryl-, alkyl- and silyl-alkynylzinc reagents to aromatic and heteroaromatic aldehydes with good yields and good to high enantioselectivities.

Enantioselective Synthesis of Unsymmetrical Benzoins from (S)-Mandelic Acid Enolate and Aromatic Aldehydes.

The reaction of the lithium enolate of the 1,3-dioxolan-4-one derived from optically active (S)-mandelic acid and pivalaldehyde with aromatic aldehydes proceeds readily to give the corresponding aldol products in good yields and diastereoselectivities. Subsequent hydroxyl protection, basic hydrolysis of the dioxolanone, oxidative decarboxylation of the α-hydroxyacid moiety, and hydroxyl deprotection provides chiral unsymmetrical benzoins with high enantiomeric excesses.

Alcohol oxidation by dioxygen and aldehydes catalysed by square-planar cobalt(III) complexes of disubstituted oxamides and related ligands

The square-planar cobalt(III) complexes of o-phenylenebis(N′-methyloxamidate) (Me2opba) and related oxamate (Meopba) and bis(oxamate) (opba) ligands catalyse the selective oxidation, by dioxygen and pivalaldehyde, of a wide range of secondary alcohols to the corresponding ketones, in good yields and under mild conditions in acetonitrile at room temperature. Thus, the oxidation of the series of α-alkylbenzyl alcohols PhCH(OH)R (R = Me, Et, iPr, tBu) results in the exclusive formation of ketones as a product of C−H bond cleavage, and no C−C bond cleavage products are observed in any case. The modulation of catalytic activity by ligand substituents among this series of cobalt catalysts highlig…

Iron(iii) oxamato-catalyzed epoxidation of alkenes by dioxygen and pivalaldehyde

A new iron(III)–carbonato monomeric complex of orthophenylenebis( oxamato) (opba) 1 is synthesized, and spectroscopically and structurally characterized; it is a moderately efficient non-heme catalyst for the aerobic epoxidation of alkenes with co-oxidation of pivalaldehyde. Ruiz Garcia, Rafael, Rafael.Ruiz@uv.es ; Fernandez Picot, Isabel, Isabel.Fernandez@uv.es ; Pedro Llinares, Jose Ramon, Jose.R.Pedro@uv.es

Novel 2-pyrone synthesis via Michael addition of mandelic acid enolate to trans-1,2-diaroylethenes

4-Aroyl-6-aryl-3-phenyl-2-pyrones are prepared in a three-step procedure involving the Michael addition of a cis-2,5-disubstituted-1,3-dioxolan-4-one, derived from mandelic acid, to trans-1,2-diaroylethenes, cyclisation to a furan under acidic conditions and lactonisation. The 2-pyrones can be also obtained directly from the Michael products under prolonged or strong acidic treatment with little decrease in yield.

Enantioselective synthesis of 2-substituted-1,4-diketones from (S)-mandelic acid enolate and α,β-enones

[EN] An approach for the synthesis of chiral non-racemic 2-substituted-1,4-diketones from (S)-mandelic acid and ¿,ß-enones has been developed. The reaction of lithium enolate of the 1,3-dioxolan-4-one derived from optically active (S)-mandelic acid and pivalaldehyde with ¿,ß-unsaturated carbonyl compounds proceeds readily to give the corresponding Michael adducts in good yields and with high diastereoselectivities. The addition of HMPA (3 equiv) reverses and strongly enhances the diastereoselectivity of the reaction. A change in the reaction mechanism from a lithium catalyzed to the one where catalysis has been suppressed by coordination of HMPA to lithium is proposed to explain these resul…

Diastereoselective Michael Addition of (S)-Mandelic Acid Enolate to Nitroalkenes. Enantioselective Synthesis of α-Hydroxy-α,β-diaryl-γ-lactams.

Abstract The reaction of the lithium enolate of the ( S , S )- cis -1,3-dioxolan-4-one derived from optically active ( S )-mandelic acid and pivalaldehyde with several aromatic nitroalkenes in the presence of HMPA proceeds readily to give the corresponding Michael adducts in good yields and diastereoselectivities. Reduction of the nitro group with Zn/HCl/EtOH/H 2 O with concomitant intramolecular aminolysis of the acetal moiety leads directly to enantiomerically pure α-hydroxy-α,β-diaryl-γ-lactams.

Ein neuartiger Eisen(III)-Komplex mit einem cyclischen Amidliganden und einer Struktur aus Schichten alternierender Chiralität

Ein organisch-metallorganisches Analogon von Tonmineralien wurde unter Cyclisierung von N,N′-Bis(ethoxalyl)phenylendiamin zu einem zweizahnigen Oxamid-Liganden (L) in basischem Medium und in Gegenwart von Eisen(III)-Ionen erhalten. Das Zusammenwirken von intramolekularen (kovalenten) Wechselwirkungen zwischen Metall und Ligand und intermolekularen (nichtkovalenten) ionischen Wechselwirkungen fuhrt dabei zu einer neuartigen Schichtverbindung mit einer faszinierenden Kristallstruktur (siehe rechts).

ChemInform Abstract: Organocatalytic Enantioselective Friedel-Crafts Alkylation of 1-Naphthol Derivatives and Activated Phenols with Ethyl Trifluoropyruvate.

Financial support from the MINECO [Gobierno de Espana and FEDER (EU)] (CTQ2013-47949-P) and from Generalitat Valenciana (ISIC2012/001) is gratefully acknowledged. M.M.-M. thanks the Universitat de Valencia for a predoctoral grant. C. V. thanks MINECO for JdC contract. Access to NMR and MS facilities from the Servei central de support a la investigacio experimental (SCSIE)-UV is also acknowledged.

Organocatalytic asymmetric addition of naphthols and electron-rich phenols to isatin-derived ketimines: highly enantioselective construction of tetrasubstituted stereocenters.

A quinine-derived thiourea organocatalyst promoted the highly enantioselective addition of naphthols and activated phenols to ketimines derived from isatins. The reaction afforded chiral 3-amino-2-oxindoles with a quaternary stereocenter in high yields (up to 99%) with excellent enantioselectivity (up to 99% ee). To the best of our knowledge, this transformation is the first highly enantioselective addition of naphthols to ketimines

Synthesis of various natural 8,12-elemanolides from artemisin

Abstract This paper describes the chemical transformations of artemisin into various natural 8,12-elemanolides.

Synthesis of Functionalized Indoles with an α-Stereogenic Ketone Moiety Through an Enantioselective Friedel-Crafts Alkylation with (E)-1,4-Diaryl-2-butene-1,4-diones

Chiral complexes of BINOL-based ligands with hafnium tert-butoxide catalyze the enantioselective Friedel-Crafts alkylation of indoles with (E)-1,4-diaryl-2-butene-1,4-diones at room temperature, with good yields and ee up to 94%. Hafnium(IV) was found to be a more effective Lewis acid than other frequently used metal ions such as titanium(IV) or zirconium(IV). Unlike the enantioselective Friedel-Crafts alkylation of indoles with α,β-unsaturated compounds where the stereogenic center is generated in the β-position to a carbonyl group, the Friedel-Crafts alkylation with 2-butene-1,4-diones described here generates an α-stereogenic center with respect to one of the carbonyl groups. This can be…

Diagnostic accuracy of elastography and magnetic resonance imaging in patients with NAFLD: A systematic review and meta-analysis

[Background and Aims] Vibration-controlled transient elastography (VCTE), point shear wave elastography (pSWE), 2-dimensional shear wave elastography (2DSWE), magnetic resonance elastography (MRE), and magnetic resonance imaging (MRI) have been proposed as non-invasive tests for patients with non-alcoholic fatty liver disease (NAFLD). This study evaluated their diagnostic accuracy for liver fibrosis and non-alcoholic steatohepatitis (NASH).

Topological control in the hydrogen bond-directed self-assembly of ortho-, meta-, and para-phenylene-substituted dioxamic acid diethyl esters

[EN] The structures of the series of N,N¿-1,n-phenylenebis(oxamic acid ethyl ester) molecules with n = 2 (H2Et2opba, 1), 3 (H2Et2mpba, 2), and 4 (H2Et2ppba, 3) have been determined by single-crystal X-ray diffraction (XRD) methods. Density functional (DF) calculations have been performed on the simplest model system N-phenyloxamic acid methyl ester (HMepma). Compounds 1¿3 have either folded (H2Et2opba), bent (H2Et2mpba), or linear (H2Et2ppba) almost planar (periplanar) molecular configurations with the two oxalamide moieties being slightly tilted up and down, respectively, with respect to the benzene ring. The energy calculations as a function of the torsion angle (¿) around the N(amide)¿C(…

Indirect regioselective heteroarylation of indoles through a Friedel–Crafts reaction with (E)-1,4-diaryl-2-buten-1,4-diones

Abstract A two-step synthesis of 3-heteroaryl indoles has been developed. The first step of the sequence involves a Friedel–Crafts alkylation of indoles with 1,4-diaryl-2-buten-1,4-diones to give the corresponding indoles bearing a 1,4-dicarbonyl moiety. The reaction is catalyzed by InCl 3 and takes place with good yields. Cyclization of the diones under different Paal–Knorr conditions allows to prepare indoles substituted at the C3 position with 3-furanyl, 3-pyrrolyl- and 3-thienyl moieties.

Lanthanum-pyBOX complexes as catalysts for the enantioselective conjugate addition of malonate esters to β,γ-unsaturated α-ketimino esters

[EN] In this paper, we report the application of chiral complexes of La(III) with pyBOX ligands as Lewis acid catalysts in the conjugate addition of malonic esters to N-tosyl imines derived from ß,gamma-unsaturated alfa-keto esters to give the corresponding chiral alfa,ß-dehydroamino esters. pyBOX complexes with La(III), Yb(III), Sc(III), and In(III) triflates were assessed in this reaction but only La(III) showed good activity and enantioselectivity, while Yb(III) provided the expected product with low yield and stereoselectivity, and the Sc(III) and In(III) complexes were completely inactive. The complex of La(OTf)3 with the diphenyl-pyBOX ligand prepared in situ provided the best results…

Sesquiterpene lactones from Centaurea alba and C. conifera

Abstract The aerial parts of Centaurea alba yielded five know germacranolides: salonitenolide, 11β, 13-dihydrosalonitenolide, salonitenolide 8- O -(4′-acetoxy-5′-hydroxy)-angelate, cnicin 4′-O-acetate and cnicin. The aerial parts of C. conifera yielded loliolide, 1β,6α-dihydroxy-4(15)-eudesmene, chlorojanerin, chlorohyssopifolin A (centaurepensin) and its C-17 epimer. The latter compound is described for the first time.

Catalytic aerobic oxidative decarboxylation of α-trifluoromethyl-α-hydroxy acids to trifluoromethyl ketones

Abstract The oxidative decarboxylation of α-trifluoromethyl-α-hydroxy acids to trifluoromethyl ketones is carried out under mild catalytic aerobic conditions using a cobalt(III) complex in the presence of pivalaldehyde.

Organocatalytic Enantioselective Friedel–Crafts Aminoalkylation of Indoles in the Carbocyclic Ring

The first general catalytic method for the, so far elusive, enantioselective Friedel−Crafts functionalization of indoles in the carbocyclic ring is presented. This transformation contrasts with the usual tendency of these heterocycles to react at the azole ring. For this purpose, the four regioisomeric hydroxy carbocyclic-substituted indoles were reacted with several isatinderived ketimines, using a Cinchona alkaloid-based squaramide, in a low 0.5−5 mol % catalyst loading, as a bifunctional catalyst. This methodology allows the functionalization of indoles in every position of the carbocyclic ring in a regio- and enantioselective fashion, by switching only the position of the hydroxy group …

ChemInform Abstract: Organocatalytic Enantioselective Aza-Friedel-Crafts Reaction of 2-Naphthols with Benzoxathiazine 2,2-Dioxides.

An organocatalytic enantioselective aza-Friedel–Crafts addition of 2-naphthols to benzoxathiazine 2,2-dioxides is described using a quinine-derived bifunctional catalyst. The method allows the use of a wide range of aromatic compounds as nucleophiles, including 1-naphthol and sesamol, and benzoxathiazines 2,2-dioxides, expanding the existing state of the art enantioselective synthesis of aminomethylnaphthol derivatives.

Chemistry and reactivity of dinuclear manganese oxamate complexes: Aerobic catechol oxidation catalyzed by high-valent bis(oxo)-bridged dimanganese(IV) complexes with a homologous series of binucleating 4,5-disubstituted-o-phennylenedioxamate ligands

[EN] The high-valent bis(oxo)-bridged dimanganese(IV) complexes with the series of binucleating 4.5-X-2-o-phenylenebis(oxamate) ligands (opbaX(2); X = H, Cl, Me) (1a-c) have been synthesized and characterized structurally, spectroscopically and magnetically. Complexes la-c possess unique Mn-2(mu-O)(2) core structures with two o-phenylenediamidate type additional bridges which lead to exceptionally short Mn-Mn distances (2.63-2.65 angstrom) and fairly bent Mn-O-Mn angles (94.1 degrees-94.6 degrees). The cyclovoltammograms of la-c in acetonitrile (25 degrees C, 0.1 M Bu4NPF6) show an irreversible one-electron oxidation peak at moderately high anodic potentials (E-ap = 0.50-0.85 V versus SCE),…

Catalytic aerobic oxidative decarboxylation of α-hydroxy-acids. Methyl mandelate as a benzoyl anion equivalent

Abstract The monomeric square-planar cobalt(III) complex of bis- N,N ′-disubstituted oxamides catalyses the oxidative decarboxylation of α-hydroxy acids with molecular oxygen/pivalaldehyde with very good yields. This reaction offers an interesting alternative in the use of methyl mandelate as a convenient benzoyl anion equivalent.

Organocatalytic Enantioselective Friedel-Crafts Alkylation of 1-Naphthol Derivatives and Activated Phenols with Ethyl Trifluoropyruvate

An organocatalytic enantioselective Friedel–Crafts alkylation of a series of substituted 1- naphthol derivatives and activated phenols with ethyl trifluoropyruvate, catalyzed by a quinine-derived squaramide, is presented. Good yields and high to excellent enantioselectivities of the Friedel– Crafts alkylation products were obtained.

A new manganese(III) oxamato dimer possesing an unprecedented Mn2(μ-O2CR)(μ-OH2⋯O2 CR) core has been synthesised, structurally and magnetically characterised, and used as a catalyst for the oxidation of alkanes to alcohols and ketones by ButO2H and O2 in CH2Cl2 at rt.

Mg/BOX complexes as efficient catalysts for the enantioselective Michael addition of malonates to β-trifluoromethyl-α,β-unsaturated ketones and their N-tosyl imines

Abstract Magnesium (II)-BOX complexes catalyze the enantioselective Michael addition of malonates to β-trifluoromethyl enones and their N-sulfonyl imines to give ketones or (E)-enamines bearing a trifluoromethylated stereogenic center, respectively, with good yields and high enantiomeric excesses. Magnesium complexes proved to be more active and stereoselective than zinc and copper analogues in these reactions.

Highly Enantioselective Friedel−Crafts Alkylations of Indoles with Simple Enones Catalyzed by Zirconium(IV)−BINOL Complexes

Complexes of BINOL-based ligands with Zr(OtBu)4 catalyze the Friedel-Crafts alkylation reaction of indoles and pyrrole with nonchelating beta-substituted alpha,beta-enones at room temperature affording the expected products with good yields and ee above 95% in most of the studied examples.

Enantioselective Henry reaction catalyzed with copper(II)–iminopyridine complexes

Abstract Copper complexes of chiral iminopyridines prepared from camphane-derived ketones and picolylamine catalyzed the enantioselective Henry (nitroaldol) reaction between nitromethane and a number of aromatic and aliphatic aldehydes with high yields and good enantioselectivities. Iminopyridines derived from (1 R )-(+)-camphor and (1 S )-(+)-ketopinic acid gave the best results to afford the opposite enantiomers in each case, despite the fact they have the same stereochemical pattern at the camphane skeleton. The reactions were carried out without air or moisture exclusion.

A solid-phase extraction liquid chromatography-tandem mass spectrometry method for the percutaneous absorption assessment of 3-(4′-methylbenzylidene)camphor via human urine analysis

The UV filter 3-(4′-methylbenzylidene)camphor (MBC) is a common ingredient in sunscreen cosmetic products. However, different in vitro and in vivo studies suggest that MBC can cause endocrine disrupting effects. This report focuses on the development of an analytical method based on solid-phase extraction (SPE) prior to liquid chromatography tandem mass spectrometry (LC-MS/MS) for the determination of MBC and its main phase I metabolite, named 3-(4′-carboxybenzylidene)camphor (CBC), in urine from users of sunscreen cosmetic products containing MBC. The formation of phase II metabolites (i.e., glucuronide and sulphate conjugates) was also considered by carrying out an enzymatic hydrolysis of…

Modular iminopyridine ligands. Application to the enantioselective copper(II)-catalyzed Henry reaction

Abstract Chiral iminopyridines prepared in a modular fashion from monoterpenic (camphor-derived) ketones and pyridinylalkylamines catalyze the enantioselective Henry (nitro aldol) reaction between nitromethane and o -anisol in the presence of copper(II) acetate, with high yields and good ee (up to 86%) under straightforward experimental conditions without the need for air or moisture exclusion.

Xanthones from Hypericum reflexum

Abstract The aerial parts of Hypericum reflexum contain six xanthones, two pyranoxanthones, two xanthonolignoids and a biphenyl. Six of these compounds are described for the first time.

Norisoprenoids from Centaurea aspera and C. salmantica

Abstract From aerial parts of Centaurea aspera var. subinermis a new homoderivative of the grasshopper ketone has been isolated. Its structure was deter

Tailoring the ligand structure to the reagent in the mandelamide-Ti(IV) catalyzed enantioselective addition of dimethyl- and diethylzinc to aldehydes

Amides derived from (S)-(+)-mandelic acid in the presence of titanium isopropoxide catalyze the enantioselective addition of dimethyl- and diethylzinc to aldehydes with good yields and ee up to 90%. Because of the modular character of the mandelamides, the structure of the ligand can be tailored to obtain the best results with each reagent. Thus, best results with dimethylzinc are obtained with N-benzyl mandelamide while N-(pyridin-2-yl) mandelamide is the best ligand for the addition of diethylzinc.

Enantioselective Synthesis of Tertiary Alcohols through a Zirconium-Catalized Friedel-Crafts Alkylation of Pyrroles with alpha-Ketoesters

Chiral complexes of 1,10-bi-2-naphthol-based ligands with zirconium tert-butoxide catalyze the Friedel Crafts alkylation of pyrroles with R-ketoesters to afford tertiary alcohols in good yields and ee up to 98%. The reaction is also of application to 4,7-dihydroindole to give C2-alkylated indoles after oxidation with p-benzoquinone.

ChemInform Abstract: Synthesis of Functionalized Indoles with an α-Stereogenic Ketone Moiety Through an Enantioselective Friedel-Crafts Alkylation with (E)-1,4-Diaryl-2-butene-1,4-diones.

Chiral complexes of BINOL-based ligands with hafnium tert-butoxide catalyze the enantioselective Friedel-Crafts alkylation of indoles with (E)-1,4-diaryl-2-butene-1,4-diones at room temperature, with good yields and ee up to 94%. Hafnium(IV) was found to be a more effective Lewis acid than other frequently used metal ions such as titanium(IV) or zirconium(IV). Unlike the enantioselective Friedel-Crafts alkylation of indoles with α,β-unsaturated compounds where the stereogenic center is generated in the β-position to a carbonyl group, the Friedel-Crafts alkylation with 2-butene-1,4-diones described here generates an α-stereogenic center with respect to one of the carbonyl groups. This can be…

ChemInform Abstract: Transformation of Artemisin Into Artapshin and 8α-Hydroxy-11β,13-Dihydrobalchanin.

Abstract Partial syntheses of the sesquiterpene lactones artapshin ( 1 ) and 8α-hydroxy-11β, 13-dihydrobalchanin ( 2 ) from artemisin ( 3 ) are described.

Organocatalytic enantioselective aminoalkylation of pyrazol-3-ones with aldimines generated in situ from α-amido sulfones

Herein, an efficient asymmetric aminoalkylation of pyrazolones with α-amido sulfones catalyzed by a quinine-derived squaramide in dichloromethane/aqueous media has been established. A variety of chiral amines were obtained with high yields (up to 98%) and excellent enantioselectivities (up to 99% ee). The corresponding products are transformed into optically active acetylated pyrazoles after treatment with Ac2O/Et3N, because of the instability of some adducts. The reaction tolerates a wide range of α-amido sulfones and different pyrazolones.

ChemInform Abstract: Catalytic Aerobic Oxidative Decarboxylation of α-Hydroxy Acids. Methyl Mandelate as a Benzoyl Anion Equivalent.

Abstract The monomeric square-planar cobalt(III) complex of bis- N,N ′-disubstituted oxamides catalyses the oxidative decarboxylation of α-hydroxy acids with molecular oxygen/pivalaldehyde with very good yields. This reaction offers an interesting alternative in the use of methyl mandelate as a convenient benzoyl anion equivalent.

Chiral bis(amino alcohol)oxalamides as ligands for asymmetric catalysis. Ti(IV) catalyzed enantioselective addition of diethylzinc to aldehydes

Abstract Several chiral bis(aminoalcohol)oxalamides with C 2 -symmetry have been prepared and used as ligands for the enantioselective addition of diethylzinc to aromatic and aliphatic aldehydes. The reaction proceeds in the presence of titanium isopropoxide to give the corresponding ( S )-alcohols with ee up to 78%. In the absence of Ti(IV), the alcohols with the opposite configuration are obtained.

ChemInform Abstract: Nucleophilic Benzoylation Using Lithiated Methyl Mandelate as a Synthetic Equivalent of the Benzoyl Carbanion. Oxidative Decarboxylation of α-Hydroxyacids.

Abstract The synthesis of alkyl aryl ketones using lithiated methyl mandelate as a synthetic equivalent of the benzoyl carbanion is reported (Umpolung). The methodology involves alkylation of methyl mandelate, hydrolysis of the ester group and oxidative decarboxylation of the resulting α-hydroxyacids. The last step is carried out in a catalytic aerobic way using a Co(III) complex in the presence of pivalaldehyde under very mild and advantageous conditions. The procedure is also applied to methyl mandelates substituted on the aromatic ring.

(S)-Mandelic acid enolate as a chiral benzoyl anion equivalent for the enantioselective synthesis of non-symmetrically substituted benzoins

A strategy for the enantioselective synthesis of non-symmetrically substituted benzoins from (S)-mandelic acid and aromatic aldehydes has been developed. This strategy is based on a diastereoselective aldol reaction of the lithium enolate of the 1,3-dioxolan-4-one derived from (S)-mandelic acid and pivalaldehyde with aromatic aldehydes, which gives the corresponding aldols in good yields. Subsequent hydroxyl group protection as MEM ethers, basic hydrolysis of the dioxolanone ring, oxidative decarboxylation of the α-hydroxy acid moiety, and hydroxyl group deprotection provides chiral non-symmetrically substituted benzoins with high enantiomeric excesses.

Sesquiterpene lactones, flavonoids and coumarins from Centaurea collina

Abstract The isolation and characterization of two coumarins, five flavonoids and four sesquiterpene lactones from the aerial parts of Centaurea collina are reported. The 13 C NMR data are included.

Enantioselective Zirconium-Catalyzed Friedel−Crafts Alkylation of Pyrrole with Trifluoromethyl Ketones

The first catalytic enantioselective Friedel-Crafts alkylation of pyrrole with 2,2,2-trifluoroacetophenones to give pyrroles with a trifluoromethyl-substituted tertiary alcohol moiety bearing a quaternary stereogenic center is described. The reaction is achieved in the presence of a 3,3'-dibromo-BINOL-Zr(IV) complex to give the expected products with high yields (up to 98%) and good enantioselectivities (up to 93% ee). The absolute stereochemistry of the products has been determined by chemical correlation.

Increased serum miR-193a-5p during non-alcoholic fatty liver disease progression: Diagnostic and mechanistic relevance

Background & Aims Serum microRNA (miRNA) levels are known to change in non-alcoholic fatty liver disease (NAFLD) and may serve as useful biomarkers. This study aimed to profile miRNAs comprehensively at all NAFLD stages. Methods We profiled 2,083 serum miRNAs in a discovery cohort (183 cases with NAFLD representing the complete NAFLD spectrum and 10 population controls). miRNA libraries generated by HTG EdgeSeq were sequenced by Illumina NextSeq. Selected serum miRNAs were profiled in 372 additional cases with NAFLD and 15 population controls by quantitative reverse transcriptase PCR. Results Levels of 275 miRNAs differed between cases and population controls. Fewer differences were seen wi…

Highly Diastereoselective Michael Reaction of (S)‐Mandelic Acid Enolate. Chiral Benzoyl Carbanion Equivalent Through an Oxidative Decarboxylation of α‐Hydroxyacids.

The reaction of the lithium enolate of the 1,3-dioxolan-4-one derived from optically active (S)-mandelic acid and pivalaldehyde with α,β-unsaturated carbonyl compounds proceeds readily to give the corresponding Michael adducts in good yields and high diastereoselectivity. Subsequent basic hydrolysis of the acetal and oxidative decarboxylation of the α-hydroxyacid moiety provides chiral 2-substituted 1,4-dicarbonyl compounds with very high enantiomeric excesses.

Transformation of artemisin into artapshin and 8α-hydroxy-11β,13-dihydrobalchanin

Abstract Partial syntheses of the sesquiterpene lactones artapshin ( 1 ) and 8α-hydroxy-11β, 13-dihydrobalchanin ( 2 ) from artemisin ( 3 ) are described.

ChemInform Abstract: Enantioselective Synthesis of Tertiary Alcohols Through a Zirconium-Catalyzed Friedel-Crafts Alkylation of Pyrroles with α-Ketoesters.

Chiral complexes of 1,1′-bi-2-naphthol-based ligands with zirconium tert-butoxide catalyze the Friedel–Crafts alkylation of pyrroles with α-ketoesters to afford tertiary alcohols in good yields and ee up to 98%. The reaction is also of application to 4,7-dihydroindole to give C2-alkylated indoles after oxidation with p-benzoquinone.

Catalytic Asymmetric Addition of Dimethylzinc to α-Ketoesters, Using Mandelamides as Ligands

[reaction: see text] A strategy based on the control of the electron-donating capabilities of the coordinating groups of the ligand has been applied in the catalytic asymmetric addition of organometallic reagents to ketoesters. Mandelamides having deprotonated alcohol and carboxyamido groups catalyzed the addition of dimethylzinc to alpha-ketoesters with good yields and ee (up to 90%).

ChemInform Abstract: Indirect Regioselective Heteroarylation of Indoles Through a Friedel-Crafts Reaction with (E)-1,4-Diaryl-2-buten-1,4-diones.

Abstract A two-step synthesis of 3-heteroaryl indoles has been developed. The first step of the sequence involves a Friedel–Crafts alkylation of indoles with 1,4-diaryl-2-buten-1,4-diones to give the corresponding indoles bearing a 1,4-dicarbonyl moiety. The reaction is catalyzed by InCl 3 and takes place with good yields. Cyclization of the diones under different Paal–Knorr conditions allows to prepare indoles substituted at the C3 position with 3-furanyl, 3-pyrrolyl- and 3-thienyl moieties.

Mandelamide-zinc-catalyzed enantioselective alkyne addition to heteroaromatic aldehydes.

The (S,S)-mandelamide III catalyzes the additions of both aryl- and alkylalkynylzinc reagents to heteroaromatic aldehydes with good yields and enantioselectivities up to 92%. This catalyst is easily prepared in a one-step procedure, and both enantiomers are available. Unlike most other described methods, using this catalyst does not require the addition of Ti(O(i)Pr)4.

ChemInform Abstract: Enantioselective Friedel-Crafts Alkylation of Indoles with (E)-1-Aryl-4-benzyloxybut-2-en-1-ones Catalyzed by an (R)-3,3′-Br2BINOLate-Hafnium(IV) Complex.

A highly enantioselective Friedel–Crafts reaction of unprotected indoles with (E)-1-aryl-4-benzyloxybut-2-en-1-ones catalyzed by a new chiral [Hf{(R)-3,3′-Br2-BINOL}(OtBu)2]2 complex has been developed to functionalize the C-3 position of the indole nucleus with a side chain bearing a 1,4-difunctionalized moiety and a benzylic stereogenic center. The reaction proceeds in good to excellent yields and excellent enantioselectivities (up to 97 % ee). The usefulness of this approach was illustrated with the synthesis of a tryptophol derivative.

Hydroxy-Directed Enantioselective Hydroxyalkylation in the Carbocyclic Ring of Indoles

[EN] A Cinchona-derived squaramide catalyzes the reaction between hydroxyindoles and isatins leading to enantioenriched indoles substituted in the carbocyclic ring. The reaction proceeds efficiently with differently substituted isatins, yielding the desired products with excellent regioselectivity, good yields, and high enantiocontroi. Moreover, every position of the carbocyclic ring of the indole can be functionalized by using the appropriate starting hydroxyindole. The OH group was removed smoothly upon hydrogenolysis of the corresponding triflate.

Enantioselective Synthesis of 2-Amino-1,1-diarylalkanes Bearing a Carbocyclic Ring Substituted Indole through Asymmetric Catalytic Reaction of Hydroxyindoles with Nitroalkenes

[EN] An asymmetric catalytic reaction of hydroxyindoles with nitroalkenes leading to the Friedel-Crafts alkylation in the carbocyclic ring of indole is presented. The method is based on the activating/directing effects of the hydroxy group situated in the carbocyclic ring of the indole providing nitroalkylated indoles functionalizated at the C-4, C-5, and C-7 positions with high yield, regio-, and enantioselectivity. The optically enriched nitroalkanes were transformed efficiently in optically enriched 2-amino-1,1-diarylalkanes bearing a carbocyclic ring substituted indole.

Nucleophilic benzoylation using a mandelic acid dioxolanone as a synthetic equivalent of the benzoyl carbanion. Oxidative decarboxylation of α-hydroxyacids

The synthesis of alkyl aryl ketones using a mandelic acid dioxolanone as a synthetic equivalent (Umpolung) of the benzoyl carbanion is reported. The methodology involves alkylation of the mandelic acid dioxolanone, hydrolysis of the dioxolanone moiety in the alkylated products and oxidative decarboxylation of the resulting alpha-hydroxyacids. The last step is carried out in a catalytic aerobic way using a Co (III) complex in the presence of pivalaldehyde under very mild conditions.

ChemInform Abstract: Highly Enantioselective Copper(I)-Catalyzed Conjugate Addition of Terminal Alkynes to 1,1-Difluoro-1-(phenylsulfonyl)-3-en-2-ones: New Ester/Amide Surrogates in Asymmetric Catalysis.

A highly enantioselective copper-catalyzed conjugate alkynylation of monoactivated enones, namely 1,1-difluoro-1-(phenylsulfonyl)-3-en-2-ones, is described. The reaction products are obtained with good yields and excellent enantioselectivities (from 92 to 99% ee). The β-alkynylated difluoro(phenylsulfonyl) ketones can be converted into the corresponding β-alkynylated difluoro- and trifluoromethyl ketones, esters and amides. This is the first example on the use of 1,1-difluoro-1-(phenylsulfonyl)-3-en-2-ones as substrates in an enantioselective reaction, which have been shown to be new ester/amide surrogates.

A Hydrogen-Bonded Supramolecular meso-Helix

[EN] A new one-dimensional hydrogen-bonded polymer with a unique meso-helical structure has been prepared from the spontaneous self-assembly in the solid-state of meta-substituted phenylene dioxamic acid diethyl ester monomers. The helical nature of this molecule and its self-complementary character, through intermolecular hydrogen bonding between oxamic acid ester functions, are the two main factors responsible for the crystalline aggregation process, as confirmed by both experimental X-ray crystallographic data and theoretical ab initio calculations.

Organocatalytic enantioselective aza-Friedel–Crafts reaction of 2-naphthols with benzoxathiazine 2,2-dioxides

An organocatalytic enantioselective aza-Friedel–Crafts addition of 2-naphthols to benzoxathiazine 2,2-dioxides is described using a quinine-derived bifunctional catalyst. The method allows the use of a wide range of aromatic compounds as nucleophiles, including 1-naphthol and sesamol, and benzoxathiazines 2,2-dioxides, expanding the existing state of the art enantioselective synthesis of aminomethylnaphthol derivatives.

Manganese(III)-mediated oxidative carbon-carbon bond cleavage of the 1,10-phenanthroline-5,6-dione ligand

[EN] A new manganese(III)-1,10-phenanthroline-5,6-dione (phendione) complex possessing a putative Mn-2(mu-O) (mu-O2CMe)(2) core has been found to undergo a Ligand-based oxidative cleavage of the C(5)-C(6) bond in weak acid aqueous MeOH under aerobic conditions at room temperature to yield 2,2'-bipyridyl-3,3'-dicarboxylate with co-reduction to the corresponding Mn-II-phendione species.

CCDC 1847752: Experimental Crystal Structure Determination

Related Article: Carles Lluna‐Galán, Gonzalo Blay, Isabel Fernández, M. Carmen Muñoz, José R. Pedro, Carlos Vila|2018|Adv.Synth.Catal.|360|3662|doi:10.1002/adsc.201800754

CCDC 1944351: Experimental Crystal Structure Determination

Related Article: Laura Carceller-Ferrer, Carlos Vila, Gonzalo Blay, Isabel Fernández, M. Carmen Muñoz, José R. Pedro|2019|Org.Biomol.Chem.|17|9859|doi:10.1039/C9OB02252J

CCDC 1402446: Experimental Crystal Structure Determination

Related Article: Marc Montesinos-Magraner, Rubén Cantón, Carlos Vila, Gonzalo Blay, Isabel Fernández, M. Carmen Muñoz, José R. Pedro|2015|RSC Advances|5|60101|doi:10.1039/C5RA11168D

CCDC 1048103: Experimental Crystal Structure Determination

Related Article: Marc Montesinos-Magraner, Carlos Vila, Rubén Cantón, Gonzalo Blay, Isabel Fernández, M. Carmen Muñoz, José R. Pedro|2015|Angew.Chem.,Int.Ed.|54|6320|doi:10.1002/anie.201501273

CCDC 1821100: Experimental Crystal Structure Determination

Related Article: Carlos Vila, Jaume Rostoll-Berenguer, Rubén Sánchez-García, Gonzalo Blay, Isabel Fernández, M. Carmen Muñoz, and José R. Pedro|2018|J.Org.Chem.|83|6397|doi:10.1021/acs.joc.8b00612

CCDC 1402447: Experimental Crystal Structure Determination

Related Article: Marc Montesinos-Magraner, Rubén Cantón, Carlos Vila, Gonzalo Blay, Isabel Fernández, M. Carmen Muñoz, José R. Pedro|2015|RSC Advances|5|60101|doi:10.1039/C5RA11168D

CCDC 1405184: Experimental Crystal Structure Determination

Related Article: Marc Montesinos-Magraner, Carlos Vila, Gonzalo Blay, Isabel Fernández, M. Carmen Muñoz and José R. Pedro|2015|Adv.Synth.Catal.|357|3047|doi:10.1002/adsc.201500548

CCDC 1439710: Experimental Crystal Structure Determination

Related Article: Marc Montesinos-Magraner, Carlos Vila, Alejandra Rendón-Patiño, Gonzalo Blay, Isabel Fernández, M. Carmen Muñoz, and José R. Pedro|2016|ACS Catalysis|6|2689|doi:10.1021/acscatal.6b00260

CCDC 1821099: Experimental Crystal Structure Determination

Related Article: Carlos Vila, Jaume Rostoll-Berenguer, Rubén Sánchez-García, Gonzalo Blay, Isabel Fernández, M. Carmen Muñoz, and José R. Pedro|2018|J.Org.Chem.|83|6397|doi:10.1021/acs.joc.8b00612

CCDC 1439713: Experimental Crystal Structure Determination

Related Article: Marc Montesinos-Magraner, Carlos Vila, Alejandra Rendón-Patiño, Gonzalo Blay, Isabel Fernández, M. Carmen Muñoz, and José R. Pedro|2016|ACS Catalysis|6|2689|doi:10.1021/acscatal.6b00260

CCDC 861026: Experimental Crystal Structure Determination

Related Article: Gonzalo Blay, Joan Cano, Luz Cardona, Isabel Fernández, M. Carmen Muñoz, José R. Pedro, and Carlos Vila|2012|J.Org.Chem.|77|10545|doi:10.1021/jo3013594

CCDC 1581116: Experimental Crystal Structure Determination

Related Article: Miguel Espinosa, Gonzalo Blay, Luz Cardona, Isabel Fernández, M. Carmen Muñoz, Jose R. Pedro|2018|J.Coord.Chem.|71|864|doi:10.1080/00958972.2018.1437422

CCDC 1048104: Experimental Crystal Structure Determination

Related Article: Marc Montesinos-Magraner, Carlos Vila, Rubén Cantón, Gonzalo Blay, Isabel Fernández, M. Carmen Muñoz, José R. Pedro|2015|Angew.Chem.,Int.Ed.|54|6320|doi:10.1002/anie.201501273

CCDC 1439709: Experimental Crystal Structure Determination

Related Article: Marc Montesinos-Magraner, Carlos Vila, Alejandra Rendón-Patiño, Gonzalo Blay, Isabel Fernández, M. Carmen Muñoz, and José R. Pedro|2016|ACS Catalysis|6|2689|doi:10.1021/acscatal.6b00260

CCDC 1530502: Experimental Crystal Structure Determination

Related Article: Marc Montesinos-Magraner, Carlos Vila, Gonzalo Blay, Isabel Fernández, M. Carmen Muñoz, José R. Pedro|2017|Org.Lett.|19|1546|doi:10.1021/acs.orglett.7b00354