Doping Efects on Ethane/Ethylene Dehydrogenation Catalyzed by Pt2X Nanoclusters.

The catalytic dehydrogenation of light alkanes is key to transform low-cost hydrocarbons to high value-added chemicals. Although Pt is extremely efficient at catalyzing this reaction, it suffers from coke formation that deactivates the catalyst. Dopants such as Sn are widely used to increase the stability and lifetime of Pt. In this work, the dehydrogenation reaction of ethane catalyzed by Pt3 and Pt2X (X=Si, Ge, Sn, P and Al) nanocatalysts has been studied computationally by means of density functional calculations. Our results show how the presence of dopants in the nanocluster structure affects its electronic properties and catalytic activity. Exploration of the potential energy surfaces show that non-doped catalyst Pt3 present low selectivity towards ethylene formation, where acetylene resulting from double dehydrogenation reaction will be obtained as a side product (in agreement with the experimental evidence). On the contrary, the inclusion of Si, Ge, Sn, P or Al as dopant agents implies a selectivity enhancement, where acetylene formation is not energetically favoured. These results demonstrate the effectiveness of such dopant elements for the design of Pt-based catalysts on ethane dehydrogenation.

Exploring the Reactivity of Rigid 1-Azadienes Derived from Methylene γ-Lactams. Applications to the Stereoselective Synthesis of Spiro-γ-Lactams.

A study on the reactivity of rigid 1-azadienes derived from methylene γ-lactams is reported. Through the functionalization of 1-amino α,ß-unsaturated γ-lactam derivatives, easily available from a multicomponent reaction of amines, aldehydes, and pyruvates, it is possible to in situ generate rigid 1-azadienes locked by a γ-lactam core. The 4π-electron system of those rigid 1-azadienes can behave as both diene and dienophile species through a spontaneous cyclodimerization reaction or exclusively as dienes or dienophiles if they are trapped with imines or cyclopentadiene, respectively. The use of chiral rigid 1-azadienes as dienophiles in the cycloaddition reaction with cyclopentadiene leads to the formation of spiro-γ-lactams bearing four stereogenic centers in a highly stereospecific manner, reporting the first example of the use of methylene-γ-lactams in the synthesis of spirocycles.

Dehydration of alcohols catalyzed by copper(II) sulfate: type II dyotropic reactions and stepwise mechanisms.

Dehydration of alcohols in the presence of copper(II) sulfate has been analyzed computationally. Density functional theory (DFT) calculations on selected alcohols indicate that this reaction can take place via two possible mechanisms: (a) concerted - although asynchronous - type II dyotropic reactions, or (b) stepwise E1-like processes, in which cleavage of the C-O bond occurs in the first step, followed by syn proton elimination. Our calculations show the relationship between the initial alcohol structure and the preferred mechanism, which is a type II dyotropic reaction for primary alcohols, whereas a stepwise process is the favored one when stable carbocation intermediates are energetically accessible. The dehydration of dehydrolinalool (2,7-dimethyl-6-en-1-yn-3-ol, DHL) to yield different alkenes of interest in the fragrance industry is discussed as a case study of its regiochemistry.

Selectivity in Cationic Cyclizations Involving Alkynes: A Computational Study on the Biomimetic Synthesis of Steroids.

Computational studies on the electrophilic cyclization between alkynes and transient carbocations or Lewis-acid-activated epoxides show that the regiochemistry of the reaction depends on the terminal or internal position of the triple bond. Reactants possessing terminal alkynyl groups lead to six-membered rings, whereas internal alkynes yield five-membered rings through 6-endo-dig and 5-exo-dig electrophilic cyclizations, respectively. The regiochemistry of the reaction is not determined by two-electron interactions, but by the minimization of Pauli repulsion. This scenario is preserved in related biomimetic reactions leading to steroid scaffolds. In this latter case, the stereochemistry of the cyclization reaction is oriented towards the formation of equatorial C-C bonds connecting the new six-six- and six-five-membered fused rings.

Selectivity in Cationic Cyclizations Involving Alkynes: A Computational Study on the Biomimetic Synthesis of Steroids.

Invited for the cover of this issue are Abel de Cózar, Ana Arrieta and Fernando P. Cossío at the University of the Basque Country. The image depicts the evolution of a reactive cation to the corresponding cyclic intermediate in the course of a regio- and stereocontrolled biomimetic cyclization. Read the full text of the article at 10.1002/chem.202204028.

Boundaries of the Hyperconjugation from π-Extended Six-Membered Phosphorus Heterocycles.

In the context of materials science, six-membered phosphorus heterocycles are intriguing building blocks due to their tunable properties through phosphorus post-functionalization and their unique hyperconjugative effects arising from the phosphorus substituents that contribute to further tuning the optoelectronic properties of the system. Seeking for the discovery of improved materials, the latter features have triggered an astonishing evolution of molecular architectures based on phosphorus heterocycles. Theoretical calculations showed that the hyperconjugation causes a reduction in the S0-S1 gap, which strongly depends on the nature of both the P-substituent and the π-conjugated core, but where are the limits? Outlining the hyperconjugative effects of six-membered phosphorus heterocycles would allow scientists to know how to design next-generation organophosphorus systems with enhanced properties. Herein, we discovered that, in cationic six-membered phosphorus heterocycles, an increase in the hyperconjugation does not affect the S0-S1 gap anymore; i.e., quaternizing the phosphorus atoms leads to properties that go beyond those provoked by hyperconjugative effects. DFT calculations revealed that the latter is particularly marked in phosphaspiro derivatives. Our detailed investigations spotlight the potential of π-extended systems based on six-membered phosphorus spiroheterocycles for accessing properties beyond those achieved to date through hyperconjugative effects, thus laying the groundwork for new research possibilities toward improved organophosphorus systems.

Synergic photoprotection of phenolic compounds present in tomato fruit cuticle: a spectroscopic investigation in solution.

Coumaric acids and flavonoids play pivotal roles in protecting plants against ultraviolet radiation (UVR) exposure. In this work, we focus our photoprotection studies on p-coumaric acid and the flavonoid naringenin chalcone. Photoprotection is well-understood in p-coumaric acid; in contrast, information surrounding photoprotection in naringenin chalcone is lacking. Additionally, and vitally, how these two species work in unison to provide photoprotection across the UV-B and UV-A is unknown. Herein, we employ transient absorption spectroscopy together with steady-state irradiation studies to unravel the photoprotection mechanism of a solution of p-coumaric acid and naringenin chalcone. We find that the excited state dynamics of p-coumaric acid are significantly altered in the presence of naringenin chalcone. This finding concurs with quenching of the p-coumaric acid fluorescence with increasing concentration of naringenin chalcone. We propose a Förster energy transfer mechanism is operative via the formation of dipole-dipole interactions between p-coumaric acid and naringenin chalcone. To our knowledge, this is the first demonstration in plants of a synergic effect between two classes of phenolics to bypass the potentially damaging effects of UVR.

Diastereoselectivity on Intramolecular Alder-ene Reaction of 1,6-Dienes.

A detailed computational study of the intramolecular Alder-ene reaction of different 1,6-dienes at M06-2X(PCM)/TZ2P level of theory has been performed. We want to understand the influence of enophile-geminal substitution pattern in the cis : trans selectivity of the cyclization process. Our analysis of the reaction coordinate by means of activation strain model of chemical reactivity (ASM-distortion interaction model) reveals that the cis-selectivity observed for unactivated reagents is related with high stabilizing orbital interaction and lower strain energy, consequence of an early transition structure. On the other hand, the presence of activating groups increases the asynchronicity of the transition structures and reduces the activation barrier due to more stabilizing orbital and electrostatic interactions, favoring trans-selectivity.

Triarylamine Enriched Organostannoxane Drums: Synthesis, Optoelectrochemical Properties, Association Studies, and Gelation Behavior.

The straightforward synthesis of three organotin clusters endowed with six triarylamine-based moieties is reported herein. The optoelectronic properties of the molecules, as well as their ability to form gels, were investigated. The association ability of the compounds was studied as well by means of variable temperature nuclear magnetic resonance (NMR) and ultraviolet-visible (UV-vis) spectroscopy. The optimization of the geometry of the compounds has been performed and compared to the X-ray diffraction of the crystals. The results obtained through this comparison are useful for the explanation of their different gelation behaviors. In fact, organostannoxane drum 1 exhibits a strong ability to form organized supramolecular structures by means of a number of noncovalent short contacts that finally yield luminescent organogels in aromatic solvents.

Does the composition in PtGe clusters play any role in fighting CO poisoning?

The high catalytic activity of Pt is accompanied by a high affinity for CO, making it extremely susceptible to poisoning. Such CO poisoning limits the use of proton exchange membrane fuel cells. In this work, using global minima search techniques and exhaustive electronic structure characterization, the dopant concentration is pinpointed as a crucial factor to improve the CO tolerance of Pt catalysts. By investigating the PtGe nanoclusters of different sizes and compositions, we found that, for those clusters with roughly the same amount of Pt and Ge, the binding to CO is weakened significantly. The uniqueness of the PtGe equimolar clusters is traced down to the electronic effects. The strong covalency and electrostatic stabilization arising from the advantageous Pt-Ge mixing make the equimolar clusters highly resistant toward CO poisoning and therefore more durable. Importantly, the novel catalysts not only are more resistant to deactivation but also remain catalytically active toward hydrogen oxidation. Representative clusters are additionally deposited on graphene with a pentagon-octagon-pentagon (5-8-5) reconstructed divacancy. The remarkable results of free-standing clusters hold true for surface mounted clusters, in which the interaction with CO is dramatically weakened for those compounds with a Pt:Ge ratio of 1:1. Our results demonstrate that Ge can be a promising alloying agent to mitigate the deactivation of Pt and that the dopant concentration is a critical factor in the design of advanced catalysts.

Probing α-Amino Aldehydes as Weakly Acidic Pronucleophiles: Direct Access to Quaternary α-Amino Aldehydes by an Enantioselective Michael Addition Catalyzed by Brønsted Bases.

The high tendency of α-amino aldehydes to undergo 1,2-additions and their relatively low stability under basic conditions have largely prevented their use as pronucleophiles in the realm of asymmetric catalysis, particularly for the production of quaternary α-amino aldehydes. Herein, it is demonstrated that the chemistry of α-amino aldehydes may be expanded beyond these limits by documenting the first direct α-alkylation of α-branched α-amino aldehydes with nitroolefins. The reaction produces densely functionalized products bearing up to two, quaternary and tertiary, vicinal stereocenters with high diastereo- and enantioselectivity. DFT modeling leads to the proposal that intramolecular hydrogen bonding between the NH group and the carbonyl oxygen atom in the starting α-amino aldehyde is key for reaction stereocontrol.

Additive and Emergent Catalytic Properties of Dimeric Unnatural Amino Acid Derivatives: Aldol and Conjugate Additions.

Different densely substituted L- and D-proline esters were prepared by asymmetric (3+2) cycloaddition reactions catalyzed by conveniently selected EhuPhos chiral ligands. The γ-nitro-2-alkoxycarbonyl pyrrolidines thus obtained in either their endo or exo forms were functionalized and coupled to yield the corresponding γ-dipeptides. The catalytic properties of these latter dimers were examined using aldol and conjugate additions as case studies. When aldol reactions were analyzed, an additive behavior in terms of stereocontrol was observed on going from the monomers to the dimers. In contrast, in the case of the conjugate additions between ketones and nitroalkenes, the monomers did not catalyze this reaction, whereas the different γ-dipeptides promoted the formation of the corresponding Michael adducts. Therefore, in this latter case emergent catalytic properties were observed for these novel γ-dipeptides based on unnatural proline derivatives. Under certain conditions stoichiometric amounts of ketone, acid and nitroalkene), formation of N-acyloxy-2-oxooctahydro-1H-indoles was observed.

Doping Platinum with Germanium: An Effective Way to Mitigate the CO Poisoning.

The vulnerability towards CO poisoning is a major drawback affecting the efficiency and long-term performance of platinum catalysts in fuel cells. In the present work, by a combination of density functional theory calculations and mass spectrometry experiments, we test and explain the promotional effect of Ge on Pt catalysts with higher resistance to deactivation via CO poisoning. A thorough exploration of the configurational space of gas-phase Ptn + and GePtn-1 + (n=5-9) clusters using global minima search techniques and the subsequent electronic structure analysis reveals that germanium doping reduces the binding strength between Pt and CO by hindering the 2π-back-donation. Importantly, the clusters remain catalytically active towards H2 dissociation. The ability of Ge to weaken the Pt-CO interaction was confirmed by mass spectrometry experiments. Ge can be a promising alloying agent to tune the selectivity and improve the durability of Pt particles, thus opening the way to novel catalytic alternatives for fuel cells.

Structure, isomerization and dimerization processes of naringenin flavonoids.

In this study, the theoretical and experimental results on the molecular structure and reactivity of the plant flavonoids naringenin chalcone and naringenin are reported. UV-vis and Raman spectra were recorded and their main bands have been assigned theoretically. Moreover, the analysis of the naringenin chalcone-naringenin cyclization-isomerization reaction and the formation of homodimers and heterodimers have been performed within a DFT framework. The presence of H-bonded water networks is mandatory to make the cyclization energetically suitable, suggesting that this equilibrium will occur in an aqueous intracellular environment rather than in the extracellular and hydrophobic plant cuticles. Additionally, the preferential formation of homodimers stabilized by π-π stacking that will interact with other dimers by H-bonding over the formation of naringenin chalcone-naringenin heterodimers is also proposed in a hydrophobic environment. These results give a plausible model to explain how flavonoids are located within the cuticle molecular arrangement.

Biological properties and conformational studies of amphiphilic Pd(II) and Ni(II) complexes bearing functionalized aroylaminocarbo-N-thioylpyrrolinate units.

A series of novel palladium(II) and nickel(II) complexes of multifunctionalized aroylaminocarbo-N-thioylpyrrolinates were synthesized and characterized by analytical and spectroscopic techniques. The biological properties of the freshly prepared compounds were screened against S. aureus, B. subtilis, A. hydrophila, E. coli, and A. baumannii bacteria and antituberculosis activity against M. tuberculosis H37Rv strains. Also, the antifungal activity was studied against C. albicans, C. tropicalis, and C. glabrata standard strains. A deep conformational survey was monitored using DFT calculations with the aim to explain the importance of the final conformation in the biological experimental results.

Effect of Remote Substituents on the Torquoselectivity of 3-Silyl Cyclobutene-Derivatives Ring-Opening Reactions.

We have quantum chemically studied the structure and nature of 1-substituted 3-trimethylsilyl cyclobutenes and 2,2-disubstituted-7-trimethylsilyl bycyclo[4.2.0]octa-1(6),3-dienes comparing their reactivity to archetypal 3-substituted cyclobutene systems using density functional theory at M06-2X(PCM)/TZ2P level. We wish to understand how the ring opening reaction is affected by a substituent not directly connected to the σ Carbon-Carbon breaking bond. To this end, we have analyzed the reaction profiles considering second order perturbation energies and natural steric analysis within NBO framework.

Dismantling the Hyperconjugation of π-Conjugated Phosphorus Heterocycles.

The development of π-extended phosphorus heterocycles has been rapidly increasing because of their unique optoelectronics properties, which are very often considered to be a consequence of special hyperconjugative interactions. However, the latter interactions have primarily been investigated within the five-membered species, phospholes, and they are often conceptually extrapolated to the rest of π-extended phosphorus heterocycles (including six-membered P-heterocycles) despite evident structural differences. Herein, we report, for the first time, a detailed investigation that sheds light on the hyperconjugative effects of a series of phosphorus heterocyclic systems by means of EDA and NBO calculations within a DFT framework. Our results lay the foundations for the future design of π-extended phosphorus heterocycles with improved optoelectronics properties.

Switching Diastereoselectivity in Catalytic Enantioselective (3+2) Cycloadditions of Azomethine Ylides Promoted by Metal Salts and Privileged Segphos-Derived Ligands.

Catalytic enantioselective 1,3-dipolar cycloaddition between imino esters and electrophilic alkenes, employing chiral metal complexes derived from copper(I) and silver(I) salts and (S)-DM- or (S)-DTBM-Segphos as ligands produces diastereodivergently exo- or endo-cycloadducts, respectively. The effect of the functional group of the dipolarophile and the fine tuning of the catalyst plays an important role in promoting reverse diastereoselectivities. The origins of experimentally observed enantioselectivity and diastereoselectivity data, as well as the origin of the observed switched endo/exo ratios, are also explained by means of density functional theory calculations.

Cooperative Catalysis with Coupled Chiral Induction in 1,3-Dipolar Cycloadditions of Azomethine Ylides.

1,3-Dipolar cycloadditions (1,3-DC) between imino esters (as precursors of N-metallated azomethine ylides) and π-deficient alkenes are promoted by cooperative asymmetric Lewis acid/Brønsted base catalysis. The components of these catalytic pairs are silver salts derived from enantiopure commercially available BINOL-based phosphoric acids and Cinchona alkaloids. Chiral phosphoric silver(I) salts promote HOMO raising of in situ formed 1,3-dipoles, whereas protonated cinchona alkaloids generate a LUMO lowering for the dipolarophiles resulting in a global acceleration of the 1,3-DC. The best results were obtained with BINOL-derived silver phosphate and hydrocinchonine. Matching between both cooperative metallo- and organocatalyst results in an enhanced enantiomeric excess, superior to that reached by both separate components. NOESY experiments and DFT calculations are compatible with a non-covalent interaction (hydrogen bond) between both catalysts, which results in close contacts and mutually coupled chiral environments.

A Three-Component Enantioselective Cyclization Reaction Catalyzed by an Unnatural Amino Acid Derivative.

A new diastereo- and enantioselective three-component cyclization reaction is described. The reaction takes place between a ketone, a carboxylic acid, and a nitroalkene to yield a bicyclic octahydro-2H-indol-2-one scaffold possessing three chiral centers. This reaction involves a rearrangement of the nitro group under simple thermal conditions. A plausible mechanism is proposed for this new reaction based on DFT calculations and isotope-labeling experiments. A new concise enantioselective synthesis of the alkaloid (+)-pancracine is presented as an example of the potential of this novel organocatalytic cyclization reaction in the synthesis of natural products.