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The enantioselective conjugate alkynylation of β-aryl-β-trifluoromethyl enones has been carried out using terminal alkynes and diethylzinc in the presence of 3,3′-bis(perfluorophenyl)BINOL as the chiral ligand to give the corresponding ketones bearing a trifluoromethylated propargylic quaternary stereocenter with fair to good enantioselectivities. Enones bearing a bulky 2-naphthyl attached to the carbonyl group provided the best enantioselectivities. The synthetic applicability of the resulting products has been demonstrated with their iodocyclization to form 4H-pyrans.

A gold-catalyzed Povarov-type reaction of fluorinated imino esters and furans is described. The process, which takes place in dichoromethane at room temperature, gives rise to novel fluorinated tetrahydrofuran-fused tetrahydroquinolines in good yields and moderate levels of diastereoselectivity in a very simple manner. The reported examples expand the versatility of the Povarov reaction to unprecedented fluorinated substrates, generating scaffolds that contain quaternary α-amino acid units.

The increase in the global atmospheric CO2 concentration resulting from over a century of combustion of fossil fuels has been associated with significant global climate change. With the global population increase driving continued increases in fossil fuel use, humanity’s primary reliance on fossil energy for the next several decades is assured. Traditional modes of carbon capture such as precombustion and postcombustion CO2 capture from large point sources can help slow the rate of increase of the atmospheric CO2 concentration, but only the direct removal of CO2 from the air, or “direct air capture” (DAC), can actually reduce the global atmospheric CO2 concentration. The past decade has seen a steep rise in the use of chemical sorbents that are cycled through sorption and desorption cycles for CO2 removal from ultradilute gases such as air. This Review provides a historical overview of the field of DAC, along with an exhaustive description of the use of chemical sorbents targeted at this application. Solv...

Financial support (Grant CTQ2013-47494-P) from the Ministerio de Economia y Competitividad (MINECO-Gobierno de Espana). A.S.M. thanks the MINECO for a predoctoral grant (FPI program). Access to NMR and MS facilities from the Servei Central de Suport a la Investigacio Experimental (SCSIE)-UV is also acknowledged.

A simple and mild protocol towards the regioselective synthesis of 1-aryl/heteroaryl-1-(2-methylimidazo[1,2-a]pyridin-3-yl)methanones has been developed by one-pot condensation of 2-aminopyridine with 1,3-diketones involving the intermediacy of 2-bromo-1,3-diketones formed in situ from 1,3-diketones using N-bromosuccinimide (NBS) in DCM by stirring at room temperature. The structure of the regioisomer has been confirmed unambiguously by the rigorous multinuclear NMR [(1H–13C) HMBC, (1H–13C) HMQC, (1H–15N) HMBC] spectroscopy and X-ray crystallographic studies.

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.

Inverse oxide/metal catalysts have shown to be excellent systems for studying the role of the oxide and oxide–metal interface in catalytic reactions. These systems can have special structural and catalytic properties due to strong oxide–metal interactions difficult to attain when depositing a metal on a regular oxide support. Oxide phases that are not seen or are metastable in a bulk oxide can become stable in an oxide/metal system opening the possibility for new chemical properties. Using these systems, it has been possible to explore fundamental properties of the metal–oxide interface (composition, structure, electronic state), which determine catalytic performance in the oxidation of CO, the water–gas shift and the hydrogenation of CO2 to methanol. Recently, there has been a significant advance in the preparation of oxide/metal catalysts for technical or industrial applications. One goal is to identify methods able to control in a precise way the size of the deposited oxide particles and their structur...

Gold(I)-catalyzed cycloisomerization of β,β-diaryl-o-(alkynyl)styrenes at 80 °C selectively yields dihydroindeno[2,1-a]indenes in a transformation that encompasses a formal [4 + 1] cycloaddition and takes place through a cascade 5-endo-cyclization–diene activation–iso-Nazarov cyclization. In addition, by performing the reaction at 0 °C, the same substrates exclusively give rise to benzofulvene derivatives, which have also been shown to be intermediates in the formation of the tetracyclics.

The catalytic activity of different supported bifunctional thioureas on sulfonylpolystyrene resins has been studied in the nitro-Michael addition of different nucleophiles to trans-β-nitrostyrene derivatives. The activity of the catalysts depends on the length of the tether linking the chiral thiourea to the polymer. The best results were obtained with the thiourea derived from (L)-valine and 1,6-hexanediamine. The catalysts can be used in only 2 mol % loading, and reused for at least four cycles in neat conditions. The ball milling promoted additions also worked very well.

The use of t-BuLi at low temperature selectively leads to α-lithiation of benzyl phenyl ether generating a stable organolithium, which can be efficiently trapped with a variety of selected electrophiles prior to suffering the expected [1,2]-Wittig rearrangement. In the case of (o-alkynyl)phenyl benzyl ethers, the intermediate α-aryloxyorganolithium undergoes an unexpected anti intramolecular carbolithiation reaction leading to functionalized benzo[b]furan derivatives.

Various indole-functionalized benzofulvene derivatives are obtained by a cascade reaction of indoles with propargylic diols involving an unusual metal-free 1,2-indole migration onto an alkyne.

A new tandem cross enyne metathesis (CEYM)–intramolecular Diels–Alder reaction (IMDAR) has been carried out. It involves conjugated ketones, esters or amides bearing a remote olefin and aromatic alkynes as the starting materials. The overall process enables the preparation of a small family of linear bicyclic scaffolds in a very simple manner with moderate to good levels of diastereoselectivity. This methodology constitutes one of the few examples that employ olefins differently than ethylene in tandem CEYM–IMDAR protocols.

A new Ir(II) complex [{Ir(μ-κCNHC,η6Dipp-IDipp)(H)}2][BF4]2 has been prepared and fully characterised. This complex acts as a catalyst for the hydroalkynylation of imines according to an unprecedented diiridium-mediated mechanism.

The conjugate diynylation of α,β-saturated trifluoromethyl ketones is carried out at low catalytic loading (2.5 mol% for aryl substituents) of a copper(I)—MeO-BIPHEP complex, triethylamine and a terminal 1,3-diyne.

Historically, many useful drugs have been developed from natural sources and their mechanisms of action deeply investigated for therapeutic applications. Recently, the interaction between pharmacologically active biomolecules and transition metal ions has opened the way to the construction of new drugs, where the unique properties of metal complexes are combined with the specific mechanisms of action of the coordinated bioligands of natural extraction. In this context, this perspective summarizes some recent research studies devoted to the development of new metal-based drugs containing Zn(II) or Cu(II) metal ions. Both metals have a strong tendency to form highly stable complexes with N,N- and O,O-donor ligands bound through chelation, giving rise, particularly when the bound organic molecules are drug candidates of natural extraction, to drug delivery systems, new biologically active complexes and potential diagnostic agents due to their intrinsic spectroscopic properties.

The Au-catalyzed chiral cycloisomerization of ortho-(alkynyl)styrenes leads to enantioenriched indenes (II), whilst the similar reaction in the presence of water or methanol affords hydroxy and methoxy derivatives (III) and (V).

The synthesis of β-thio substituted carbonyl compounds is achieved by uncatalyzed reaction of α,β-unsaturated carbonyl compounds with thiodioxaborolanes under mild reaction conditions.

Rhodium complexes featuring one or two trifluoroacetato ligands catalyze the unusual formation of a variety of α-vinylsilanes in good selectivities by non-directed hydrosilylation of terminal alkynes.

In the presence of NFA, the process is finished after 10 min with good to excellent yields.

A short and convenient synthesis of fused 1,2,5-selenadiazoles from the corresponding 1,2,5-thiadiazoles and selenium dioxide has been developed.

The new title compound is precipitated from a stoichiometric aqueous solution of NiCl2 and NaF (60 °C, 6 h).

Imines generated in situ from salicylaldehydes react with sodium borohydride, methanol, and a second equivalent of aldehydes to form fairly stable cyclic boramides.

Several 8-oxabicyclo[3.2.1]oct-6-en-3-ones are prepared by cycloaddition reaction of chiral furanes such as (I) and (VII) with dibromoketone (II).

Fluorinated 2-(p-tolylsulfinyl)benzyl carbanions react with allyl and propargyl halides in a highly stereoselective way, providing homoallylic and homopropargylic fluorides, respectively, with high optical purity. Theoretical calculations found transition states for these transformations whose relative stabilities are consistent with the experimentally observed stereoselectivity.

Attempts to synthesize 2-hydroxynitrostyrenes by a Knoevenagel condensation of salicylaldehyde and subsequent elimination were unsuccessful because of the formation of a stable imine. This could be easily prevented by using secondary amines to catalyze the reaction, which then afforded 2-hydroxynitrostyrenes in high yields. In addition, the stable imine that was formed by employing ammonium acetate underwent a reaction with phosgene to allow the preparation of benzoxazines in good yields.

This method yields diborylated products which can be directly converted to the corresponding alcohols.

Activated olefins directly react with phenylselenium borane (II) without any metal or organocatalytic assistance.

Diphenylsilylprolinol is demonstrated to be an efficient catalyst for sulfonyl analogue Nazarov reagents (I) to afford chiral cyclohexa-1,3-dienes in a Diels—Alder reaction manner.

The regioselectivity of the reaction of tosyloxyketones (I) with N-substituted thioureas (II) is strongly influenced by the substituents.

Aryl and alkyl aldehydes react with phosphites in the presence of squaramides to α-hydroxy phosphonates in good yields and high enantioselectivities.

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.

The first enantioselective conjugate alkynylation of β-trifluoromethyl α,β-enones (II) using terminal alkynes (I) and a taniaphos-Cu(I) complex as catalyst is described.

Tetrafluorinated analogues of both UDP-galactopyranose and UDP-galactofuranose have been synthesized and assayed against UDP-galactopyranose mutase, a key enzyme for Mycobacterium tuberculosis cell wall biosynthesis. Competition assays and STD-NMR spectroscopy techniques have evidenced not only the first unambiguous case of affinity enhancement through local sugar polyfluorination, but also showed that tetrafluorination can still have a beneficial effect on binding when monofluorination at the same position does not.

In this article, a complete study on the selectivity of titanocene(III) cyclization of epoxypolyprenes is presented. The requirements for the formation of six- or seven-membered rings during these cyclizations are determined, taking into account the different substitution pattern in the epoxypolyprene precursor. Thus, a complete selectivity to 6-exo or 7-endo cyclization process has been achieved, yielding mono-, bi-, and even tricyclic compounds, constituting a new and efficient access to this type of derivative. Additionally, this procedure opens the possibility to prepare excellent building blocks for the synthesis of polycyclic compounds with a trisubstituted oxygenated function, which is present in several natural terpenes.

Benzo[a]quinolizine is an important heterocyclic framework that can be found in numerous bioactive compounds. The general scheme for the synthesis of these compounds was based on the preparation of the appropriate dihydroisoquinolines by Bischler-Napieralski cyclization with good yields, followed by the Pemberton method to form the oxazinones or pyridones derivatives via acyl-ketene imine cyclocondensation. All the synthesized compounds were assayed in vitro for their ability to inhibit mitochondrial respiratory chain. Most of the tested compounds were able to inhibit the integrated electron transfer chain, measured as NADH oxidation, which includes complexes I, III and IV, in the low micromolar range. Oxazino[2,3-a]isoquinolin-4-ones displayed greater activity than their pyrido[2,1-a]isoquinolin-4-ones analogs. Indeed, the presence of a furan ring in C₂ position of oxazino[2,3-a]isoquinolin-4-ones provided the compound (1g) with the most potent biological activity. Therefore, these compounds and especially the oxazinone derivatives are in the tendency of the new less toxic antitumor agents that target mitochondrial electron transport chain in a middle range potency.

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" contracts

The title reaction proceeds with total chemoselectivity towards polyfunctionalized allyl boronates (III), (V), and (VII).

Gold-catalyzed cyclization of 1,3-dien-5-ynes in the presence of alcohols produces highly substituted cyclopentadienes in good yields.

Polyhydroxylated pyrrolidines are synthesized in a one-pot procedure by addition of an organometallic reagent to isoxazolidines obtained by 1,3-dipolar cycloaddition between nitrones and vinylsulfones.