Dichlorodioxomolybdenum(VI) complexes: useful and readily available catalysts in organic synthesis

Molybdenum(VI) dichloride dioxide (MoO2Cl2), and its addition complexes [MoO2Cl2(L)n; L = neutral ligand], are commercially or easily available and inexpensive transition-metal complexes based on a non-noble metal that can be applied as catalysts for various organic transformations. This short review aims to present the most significant breakthroughs in this field.Ministerio de Economía y Competitividad (MINECO) (CTQ2016-48937-C2-1-P) and Junta de Castilla y León and FEDER (BU076U16

Synthesis of α-functionalized α-indol-3-yl carbonyls through direct SN reactions of indol-3-yl α-acyloins

A new and efficient synthesis of α-functionalized α-indol-3-yl ketones from easily available indolyl α-acyloins is reported. This process, catalyzed by Brønsted or Lewis acids, involves an uncommon direct nucleophilic substitution reaction of a secondary α-carbonyl-substituted hydroxyl group. The described methodology allows the introduction of a variety of nucleophiles such as (hetero)arenes, thiophenols, nitroanilines and 1,3-dicarbonyl derivatives. The synthesized α-indol-3-yl carbonyl compounds are important synthetic targets also useful for accessing functionalized tryptophols and furan-3-yl indoles.Ministerio de Economía y Competitividad (MINECO) (CTQ2013-48937-C2-1-P) and Junta de Castilla y León and FEDER (BU237U13 and BU076U16

Asymmetric Gold(I)‐Catalyzed Tandem Hydroarylation–Nazarov Cyclization: Enantioselective Access to Cyclopentenones

The asymmetric synthesis of cyclopentachromenones from gold-catalyzed reaction of readily available skipped alkenynones is described. This cascade reaction involves an initial anti-Michael hydroarylation of the ynone moiety to form a gold-functionalized dialkenylketone intermediate, followed by a Nazarov cyclization that proceeds in an unprecedented enantioselective manner. Excellent enantiomeric ratios and chemical yields are obtained under mild reaction conditions.We gratefully acknowledge Ministerio de Ciencia e Innovación and FEDER (CTQ2016-75023-C2-1-P and PID2020- 115789GB-C21), and Junta de Castilla y León and FEDER (BU291P18 and BU049P20) for financial support. The project leading to these results has received funding from “la Caixa” Foundation, under the Agreement LCF/PR/ PR18/51130007> (CAIXA-UBU001). M.S. and S.S.-P. thank Junta de Castilla y León (Consejería de Educación) and Fondo Social Europeo (ESF+) for a predoctoral and a postdoctoral contract, respectively

Gold-Catalyzed Synthesis of 1-(Indol-3-yl)carbazoles: Selective 1,2-Alkyl vs 1,2-Vinyl Migration

Gold(III)-catalyzed cycloisomerization of α-bis(indol-3-yl)methyl alkynols selectively affords 1-(indol-3-yl)carbazoles, in a transformation that takes place through a selective 1,2-alkyl vs 1,2-vinyl migration step in the vinyl-gold intermediate generated from the initial 5-endo-spirocyclization. The reaction proceeds well with either tertiary or secondary starting alkynols as well as with a wide variety of alkyne substituents. The key role of the other indol-3-yl substituent for the unexpected selectivity in the 1,2 rearrangement has also been supported by DFT calculations that reveal a low barrier, two-step mechanism in the alkyl migration path where the second indole significantly stabilizes a carbocationic intermediate.Junta de Castilla y León and FEDER (BU076U16) and Ministerio de Economía y Competitividad (MINECO) (CTQ2016-75023-C2-1-P and CTQ2016-75023- C2-2-P

1,5-O → N Carbamoyl Snieckus–Fries-Type Rearrangement

The reaction of o-lithiated O-aryl N,N-diethylcarbamates with (hetero)aromatic nitriles gives rise to functionalized salicylidene urea derivatives in high yields through a new 1,5-O → N carbamoyl migration. This Snieckus–Fries-type rearrangement nicely complements previously known O → C and O → O related shifts. In addition, when dimethylmalononitrile is used as the electrophilic partner, the carbamoyl shift is preferred over the expected transnitrilation reaction.Junta de Castilla y León and FEDER (BU076U16) and Ministerio de Economía y Competitividad (MINECO) and FEDER (CTQ2016-48937-C2-1-P

Merging α-Lithiation and Aldol-Tishchenko Reaction to Construct Polyols from Benzyl Ethers

α-Lithiobenzyl ethers, generated by selective α-lithiation, undergo an aldol-Tishchenko reaction upon treatment with carboxylic esters and paraformaldehyde. The reaction of the organolithium with the carboxylate generates an intermediate enolate that, after formaldehyde addition, affords 1,2,3-triol derivatives in a straightforward and one-pot manner. These products are obtained as single diastereoisomers bearing a quaternary stereocenter. The complete diastereocontrol of the aldol-Tishchenko process is attributed to stereoelectronic preferences in the transition state.Ministerio de Ciencia e Innovación and FEDER (CTQ2016-75023-C2-1-P) and Junta de Castilla y León and FEDER (BU291P18

1,3-Dien-5-ynes: Versatile Building Blocks for the Synthesis of Carbo- and Heterocycles

1,3-Dien-5-ynes have been extensively used as starting materials for the synthesis of a wide number of different carbo- and heterocycles. The aim of this review is to give an overview of their utility in organic synthesis, highlighting the variety of compounds that can be directly accessed from single reactions over these systems. Thus, cycloaromatization processes are initially commented, followed by reactions directed toward the syntheses of five-membered rings, other carbocycles and, finally, heterocycles. The diverse methodologies that have been developed for the synthesis of each of these types of compounds from 1,3-dien-5-ynes are presented, emphasizing the influence of the reaction conditions and the use of additional reagents in the outcome of the transformations.Ministerio de Economía y Competitividad (MINECO) and FEDER (CTQ2013-41336-P, CTQ2013- 48937-C2-1-P, and CTQ2014-52488-R), Universidad de Alcalá (CCG2015/EXP-003) and Junta de Castilla y León (BU237U13

Regioselective synthesis of elusive 4,9-Dihydro-1H-Carbazoles by gold-catalyzed cycloisomerization of 3-Allenylmethylindoles

A general and efficient synthesis of 4,9-dihydro- 1H-carbazoles from 3-allenylmethylindoles is reported. The process, catalyzed by a cationic gold(I) complex, involves a formal C2−H bond activation of the indole unit by reaction with the allene. The nature of the substituents at the allylic and terminal positions of the allene moiety has a crucial effect on the regioselectivity of the cyclization, which is also influenced by the catalyst and the solvent employed. Moreover, some evidence of the contribution of different reaction routes is provided, which led us to propose a plausible multipathway mechanism consistent with all of the results described.MICINN and FEDER (CTQ2010-15358 and CTQ2009-09949/BQU) for financial support. E.A. thanks MEC for an FPU predoctoral fellowship. P.G.-G. and M.A.F.-R. thank MICINN for "Juan de la Cierva" and "Ramon y Cajal" contractsThis document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of organic chemistry, copyright © American Chemical Society after peer review and technical editing by the publisher

Brønsted acid−catalyzed synthesis of tetrasubstituted allenes and polysubstituted 2H-chromenes from tertiary propargylic alcohols

A practical and environmentally benign Brønsted acid−catalyzed protocol for the preparation of all-carbon tetrasubstituted allenes, consisting in the direct SNˈ addition of tri- or dimethoxy arenes or allyltrimethylsilane to tertiary propargylic alcohols, has been developed. In addition, a straightforward synthesis of densely substituted 2H-chromenes by metal-free tandem allenylation/heterocyclization reaction of methoxyphenols and tertiary alkynols is presented.Junta de Castilla y León and FEDER (BU291P18) and Ministerio de Economía y Competitividad (MINECO) and FEDER (CTQ2016-75023-C2-1-P

Uso de un compuesto de fórmula (I) como bactericida frente a Streptococcus

Uso de al menos un compuesto de fórmula (I) donde R1 es alquilo C1-C6 o forma Ncicloalquilo C5-C8 junto con R2 ; R 2 es alquilo C1-C6, forma Ncicloalquilo C5-C8 junto con R1 , o es una cadena alquílica que se une a (CH2)n formando una amina bicíclica; R3 es alquilo C1-C2 o ausente; R4 es un sustituyente aromático que comprende al menos dos anillos aromáticos; n es un valor entre 1 y 2; y m es un valor entre 0 y 1; como bactericida frente a Streptococcus, preferiblemente frente a Streptococcus pneumoniae. Adicionalmente, compuesto de fórmula (Ia) y una composición bactericida que lo comprenda.Peer reviewedConsejo Superior de Investigaciones Científicas, Universidad Miguel HernándezB1 Patente sin examen previ