Deciphering the Reactive Pathways of Competitive Reactions inside Carbon Nanotubes.

Nanoscale control of chemical reactivity, manipulation of reaction pathways, and ultimately driving the outcome of chemical reactions are quickly becoming reality. A variety of tools are concurring to establish such capability. The confinement of guest molecules inside nanoreactors, such as the hollow nanostructures of carbon nanotubes (CNTs), is a straightforward and highly fascinating approach. It mechanically hinders some molecular movements but also decreases the free energy of translation of the system with respect to that of a macroscopic solution. Here, we examined, at the quantum mechanics/molecular mechanics (QM/MM) level, the effect of confinement inside CNTs on nucleophilic substitution (SN2) and elimination (syn-E2 and anti-E2) using as a model system the reaction between ethyl chloride and chloride. Our results show that the three reaction mechanisms are kinetically and thermodynamically affected by the CNT host. The size of the nanoreactor, i.e., the CNT diameter, represents the key factor to control the energy profiles of the reactions. A careful analysis of the interactions between the CNTs and the reactive system allowed us to identify the driving force of the catalytic process. The electrostatic term controls the reaction kinetics in the SN2 and syn/anti-E2 reactions. The van der Waals interactions play an important role in the stabilization of the product of the elimination process.

Allylic and Allenylic Dearomatization of Indoles Promoted by Graphene Oxide by Covalent Grafting Activation Mode.

The site-selective allylative and allenylative dearomatization of indoles with alcohols was performed under carbocatalytic regime in the presence of graphene oxide (GO, 10 wt % loading) as the promoter. Metal-free conditions, absence of stoichiometric additive, environmentally friendly conditions (H2 O/CH3 CN, 55 °C, 6 h), broad substrate scope (33 examples, yield up to 92 %) and excellent site- and stereoselectivity characterize the present methodology. Moreover, a covalent activation model exerted by GO functionalities was corroborated by spectroscopic, experimental and computational evidences. Recovering and regeneration of the GO catalyst through simple acidic treatment was also documented.

Electron Dynamics with Explicit-Time Density Functional Theory of the [4+2] Diels-Alder Reaction.

The prototype Diels-Alder (DA) reaction between butadiene and ethene (system 1) and the DA reaction involving 1-methoxy-butadiene and cyano-ethylene (system 2) are investigated with an explicit-time-dependent Density Functional Theory approach. Bond orders and atomic net charges obtained in the dynamics at the transition state geometry and along the reaction coordinate toward reactants are used to provide a picture of the process in terms of VB/Lewis resonance structures that contribute to a resonance hybrid. The entire dynamics can be divided into different domains (reactant-like, product-like, and transition state domains) where different Lewis resonance structures contribute with different weights. The relative importance of these three domains varies along the reaction coordinate. In addition to the usual reactant-like and product-like covalent Lewis structures, ionic Lewis structures have non-negligible weights. In system 2, the electron-donor OCH3 on the diene and the electron-acceptor CN on the dienophile make more important the contributions of ionic Lewis structures that stabilize the transition state and determine the decrease of the reaction barrier with respect to system 1.

Proposta de um plano de gestão por processos para o alcance da meta calórica diária de pacientes em condições clínicas adversas / Process based management plan to enable patients in adverse clinical conditions reach the daily caloric target

Objetivos ­ Apresentar um modo de gestão por processos coordenados à assistência nutricional, por meio da equipe de terapia multiprofissional (EMTN), alinhando o plano terapêutico a fim de se atingir as metas energético-proteicas dos pacientes, e assim, manter o gerenciamento de dados para o indicador de qualidade. O controle de qualidade em terapia nutricional deve ser realizado por meio de instrumentos de monitorização periódica pré-estabelecidos, almejando alcançar os objetivos e as metas propostas, assim como identificar a problemática e criar estratégias e normativas de gerenciamento. Métodos ­ O processo de gestão foi implementado em dois hospitais privados de grande porte da cidade de São Paulo, os dados foram coletados pela equipe multiprofissional de terapia nutricional (EMTN) diariamente, compilados em planilhas e os resultados discutidos mensalmente durante reuniões administrativas da equipe, sendo proposto planos de ação para melhorias permanentes. Resultados ­ O plano de ação proposto no presente trabalho se mostrou sensível quanto à detecção e identificação de intercorrências durante a terapia nutricional e também se mostrou como uma ferramenta importante para o estabelecimento de um plano de ação tendo como reflexo uma equipe de EMTN continuamente treinada e atenta para corrigir possíveis falhas. Conclusões ­ A adequação da rotina a partir do plano de gestão como o proposto nesse estudo é uma ferramenta importante para o alcance das metas energéticos-protéicas dos pacientes e manutenção do gerenciamento de dados e indicadores de qualidade

Objetives ­ To present a process-based management method in which nutritional care is coordinated by a multidisciplinary nutrition therapy team (MNTT), whereby the therapeutic plan is tailored to meet patient energy and protein requirements and manage data, thus allowing for the monitoring of quality indicators. The management process was implemented in two large private hospitals in the city of São Paulo, SP, Brazil. Quality control of nutrition therapy should be performed using validated periodic monitoring instruments that allow health professionals to identify problems and devise appropriate solutions and management regulations in order to achieve proposed objectives and goals. Methods ­ Data was collected on a daily basis by the MNTT and compiled in spreadsheets. The results were discussed at monthly administrative team meetings, and action plans were drawn up to promote permanent improvements. Results ­ The action plan proposed by the present study was able to detect complications that arise during nutrition therapy and proved to be an important tool for tailoring nutrition therapy to meet patient protein and energy requirements, being supported by a continuously trained and attentive MNTT that is qualified to correct possible flaws. Conclusions ­ The adequacy of the routine from the management plan as proposed in this study is an important tool to reach the patient's protein-energy goals and maintenance of data management and quality indicators

DNAzymes at Work: A DFT Computational Investigation on the Mechanism of 9DB1.

The 9DB1 DNAzyme follows an addition-elimination (AN+DN) two-step mechanism, involving a phosphorane intermediate, where the 3'-hydroxyl group (nucleophile) of one RNA fragment attacks the 5'-triphosphate of another RNA fragment. This mechanism does not involve a divalent metal cation in agreement with the experimental evidence. The process is assisted by two proton transfers that activate the nucleophile (first step) and the leaving group (second step). The dA13 nucleotide is not directly involved in the reaction. However, it plays an important role in determining the regioselectivity of the process: since the dA13 phosphate forms a strong hydrogen bond with the 2'-hydroxyl, only the 3'-hydroxyl can behave as a nucleophile and form the new 3'-5' bond. In silico mutagenesis, where the dA13 phosphate oxygen involved in the hydrogen contact was replaced by a sulfur atom, causes a significant rearrangement of the A50 ribose position with an increase in the activation barrier and a consequent lower enzymatic activity in agreement with the experimental evidence. A similar effect is determined by the replacement of the 2'-hydroxyl with different groups such as F, H, and OMe.

Stable and Biocompatible Monodispersion of C60 in Water by Peptides.

The lack of solubility in water and the formation of aggregates hamper many opportunities for technological exploitation of C60. Here, different peptides were designed and synthesized with the aim of monomolecular dispersion of C60 in water. Phenylalanines were used as recognizing moieties, able to interact with C60 through π-π stacking, while a varying number of glycines were used as spacers, to connect the two terminal phenylalanines. The best performance in the dispersion of C60 was obtained with the FGGGF peptidic nanotweezer at a pH of 12. A full characterization of this adduct was carried out. The peptides disperse C60 in water with high efficiency, and the solutions are stable for months both in pure water and in physiological environments. NMR measurements demonstrated the ability of the peptides to interact with C60. AFM measurements showed that C60 is monodispersed. Electrospray ionization mass spectrometry determined a stoichiometry of C60@(FGGGF)4. Molecular dynamics simulations showed that the peptides assemble around the C60 cage, like a candy in its paper wrapper, creating a supramolecular host able to accept C60 in the cavity. The peptide-wrapped C60 is fully biocompatible and the C60 "dark toxicity" is eliminated. C60@(FGGGF)4 shows visible light-induced reactive oxygen species (ROS) generation at physiological saline concentrations and reduction of the HeLa cell viability in response to visible light irradiation.

Graphene Oxide Promotes Site-Selective Allylic Alkylation of Thiophenes with Alcohols.

The graphene oxide (GO) assisted allylic alkylation of thiophenes with alcohols is presented. Mild reaction conditions and a low GO loading enabled the isolation of a range of densely functionalized thienyl and bithienyl compounds in moderate to high yields (up to 90%). The cooperative action of the Brønsted acidity, epoxide moieties, and π-surface of the 2D-promoter is highlighted as crucial in the reaction course of the present Friedel-Crafts-type protocol.

Proteins as supramolecular hosts for C60: a true solution of C60 in water.

Hybrid systems have great potential for a wide range of applications in chemistry, physics and materials science. Conjugation of a biosystem to a molecular material can tune the properties of the components or give rise to new properties. As a workhorse, here we take a C60@lysozyme hybrid. We show that lysozyme recognizes and disperses fullerene in water. AFM, cryo-TEM and high resolution X-ray powder diffraction show that the C60 dispersion is monomolecular. The adduct is biocompatible, stable in physiological and technologically-relevant environments, and easy to store. Hybridization with lysozyme preserves the electrochemical properties of C60. EPR spin-trapping experiments show that the C60@lysozyme hybrid produces ROS following both type I and type II mechanisms. Due to the shielding effect of proteins, the adduct generates significant amounts of 1O2 also in aqueous solution. In the case of type I mechanism, the protein residues provide electrons and the hybrid does not require addition of external electron donors. The preparation process and the properties of C60@lysozyme are general and can be expected to be similar to other C60@protein systems. It is envisaged that the properties of the C60@protein hybrids will pave the way for a host of applications in nanomedicine, nanotechnology, and photocatalysis.

C60 Bioconjugation with Proteins: Towards a Palette of Carriers for All pH Ranges.

The high hydrophobicity of fullerenes and the resulting formation of aggregates in aqueous solutions hamper the possibility of their exploitation in many technological applications. Noncovalent bioconjugation of fullerenes with proteins is an emerging approach for their dispersion in aqueous media. Contrary to covalent functionalization, bioconjugation preserves the physicochemical properties of the carbon nanostructure. The unique photophysical and photochemical properties of fullerenes are then fully accessible for applications in nanomedicine, sensoristic, biocatalysis and materials science fields. However, proteins are not universal carriers. Their stability depends on the biological conditions for which they have evolved. Here we present two model systems based on pepsin and trypsin. These proteins have opposite net charge at physiological pH. They recognize and disperse C60 in water. UV-Vis spectroscopy, zeta-potential and atomic force microscopy analysis demonstrates that the hybrids are well dispersed and stable in a wide range of pH’s and ionic strengths. A previously validated modelling approach identifies the protein-binding pocket involved in the interaction with C60. Computational predictions, combined with experimental investigations, provide powerful tools to design tailor-made C60@proteins bioconjugates for specific applications.

Functionalization Pattern of Graphene Oxide Sheets Controls Entry or Produces Lipid Turmoil in Phospholipid Membranes.

Molecular dynamics, coarse-grained to the level of hydrophobic and hydrophilic interactions, shows that graphene oxide sheets, GOSs, can pierce through the phospholipid membrane and navigate the double layer only if the hydrophilic groups are randomly dispersed in the structure. Their behavior resembles that found in similar calculations for pristine graphene sheets. If the oxidation is located at the edge of the sheets, GOSs hover over the membrane and trigger a major reorganization of the lipids. The reorganization is the largest when the radius of the edge-functionalized sheet is similar to the length of the lipophilic chain of the lipids. In the reorganization, the heads of the lipid chains form dynamical structures that pictorially resemble the swirl of water flowing down a drain. All effects maximize the interaction between hydrophobic moieties on the one hand and lipophilic fragments on the other and are accompanied by a large number of lipid flip-flops. Possible biological consequences are discussed.

A Full QM Computational Study of the Catalytic Mechanism of α-1,4-Glucan Lyases.

We investigated the catalytic mechanism of α-1,4-glucan lyases using a full QM DFT approach based on the M06-2X functional. The reaction profile of the whole catalytic process can be divided into three phases: glycosylation, deglycosylation-elimination and tautomerization. Glycosylation is a highly asynchronous SN 1-like process with an energy barrier of 10.2 kcal mol-1 . A proton moves from the Asp665 residue to the glycosidic oxygen. Asp553 acts as a nucleophile and attacks the anomeric carbon causing the cleavage of the glycosidic bond. Deglycosilation-elimination is the rate-determining step of the entire process with an overall barrier of 18.3 kcal mol-1 . The final step (restoring the catalyst and tautomerization) occurs rather easily, since the Asp553 carboxylate group "assists" the proton transfer in the tautomerization process. Our computations clearly indicate that tautomerization must occur inside the enzyme before leaving the active site rather than in the aqueous solution. Outside of the protein environment the enol-AF→keto-AF process "assisted" by a water molecule has a barrier of 35.8 kcal mol-1 .

Nutrition therapy: A new criterion for treatment of patients in diverse clinical and metabolic situations.

OBJECTIVE: This study developed an instrument in table format to help determine the energy requirements of patients in adverse situations. The instrument allows for the weekly adjustment of nutrition therapy and energy intake, advocating a new approach to treatment based on clinical observation performed by staff specialized in individualized nutrition therapy. METHODS: The table was elaborated by grouping patients according to the following criteria: criticality, chronicity, and stability of the clinical status. Energy supply was readjusted weekly to respect the cyclicity of the patient's metabolic response. RESULTS: The table should be used in the following order: Obese > Elderly > Specific Clinical Situations > Chronic Diseases > Stable Clinical Situations. The protein requirements of patients with pressure ulcers or with wounds healing by secondary intention should be increased by 30% to 50%. Current patient weight should always be used, except in patients with anasarca. In these cases, the patient's last known dry weight or the ideal weight should be used. For elderly patients whose weight is not known and who cannot be weighed because of the patient's clinical condition, a body mass index of 23 should be assumed. CONCLUSION: The proposed nutrition table allows for management of optimal energy and protein intake for patients in different clinical situations, while respecting the different phases of the posttraumatic metabolic response, thus leading to favorable clinical outcomes.

Nutritional and microbiological quality of commercial and homemade blenderized whole food enteral diets for home-based enteral nutritional therapy in adults.

BACKGROUND & AIMS: Serious nutritional and contamination risks may be involved in the preparation of blenderized tube-feeding diets and in the handling of commercial diets. Their nutritional and microbiological quality in home settings is unknown. The objective of this study was to assess the nutritional and microbiological quality of commercial enteral and homemade blenderized whole foods diets intended to adult patients in home nutritional therapy. METHODS: In a cross sectional study, 66 samples of commercial (CD) and noncommercial (NCD) enteral diets were collected at the homes of patients in home enteral nutritional therapy, 33 of each type. Commercial diets were either powder (PCD; n = 13) or liquid (LCD; n = 20). The samples were analyzed in laboratory to assess their nutritional and microbiological quality. Anthropometric data of mid upper arm circumference (MUAC) and triceps skinfold (TST) thickness were obtained from the patients' medical records. RESULTS: NCD presented significantly lower values for protein, fat, fiber, carbohydrate and energy while water content was significantly higher. PCD and LCD did not show any statistically significant differences between them. In the NCD, the values measured for macronutrients and energy corresponded to less than 50% of the prescribed values (except for fat). In CD, protein value was about 20% more than the prescribed value; fat and energy values corresponded to approximately 100% of the prescription, while carbohydrate corresponded to 92%. Regardless the type of the diet, prevalence of undernutrition was high in both groups though patients of the NCD presented a higher percentage. Samples of NCD complied significantly less with the microbiological standards; only 6.0% complied with the standard for coliform bacteria. Escherichia coli was detected in 10, 2, and 2 samples of NCD, PCD and LCD, respectively. CONCLUSIONS: Homemade blenderized enteral diets showed low values of energy and macronutrients, delivered less than 50% of the prescribed values and had high levels of bacterial contamination.

Interactions between Endohedral Metallofullerenes and Proteins: The Gd@C60-Lysozyme Model.

Endohedral metallofullerenes (EMFs) have great potential as radioisotope carriers for nuclear medicine and as contrast agents for X-ray and magnetic resonance imaging. EMFs have still important restrictions for their use due to low solubility in physiological environments, low biocompatibility, nonspecific cellular uptake, and a strong dependence of their peculiar properties on physiological parameters, such as pH and salt content. Conjugation of the EMFs with proteins can overcome many of these limitations. Here we investigated the thermodynamics of binding of a model EMF (Gd@C60) with a protein (lysozyme) that is known to act as a host for the empty fullerene. As a rule, even if the shape of an EMF is exactly the same as that of the related fullerene, the interactions with a protein are significantly different. The estimated interaction energy (ΔG binding) between Gd@C60 and lysozyme is -18.7 kcal mol-1, suggesting the possibility of using proteins as supramolecular carriers for EMFs. π-π stacking, hydrophobic interactions, surfactant-like interactions, and electrostatic interactions govern the formation of the hybrid between Gd@C60 and lysozyme. The comparison of the energy contributions to the binding between C60 or Gd@C60 and lysozyme suggests that, although shape complementarity remains the driving force of the binding, the presence of electron transfer from the gadolinium atom to the carbon cage induces a charge distribution on the fullerene cage that strongly affects its interaction with the protein.

Aggregation Pathways of Native-Like Ubiquitin Promoted by Single-Point Mutation, Metal Ion Concentration, and Dielectric Constant of the Medium.

Ubiquitin-positive protein aggregates are biomarkers of neurodegeneration, but the molecular mechanism responsible for their formation and accumulation is still unclear. Possible aggregation pathways of human ubiquitin (hUb) promoted by both intrinsic and extrinsic factors, are here investigated. By a computational analysis, two different hUb dimers are indicated as possible precursors of amyloid-like structures, but their formation is disfavored by an electrostatic repulsion involving Glu16 and other carboxylate residues present at the dimer interface. Experimental data on the E16V mutant of hUb shows that this single-point mutation, although not affecting the overall protein conformation, promotes protein aggregation. It is sufficient to shift the same mutation by only two residues (E18V) to regain the behavior of wild-type hUb. The neutralization of Glu16 negative charge by a metal ion and a decrease of the dielectric constant of the medium by addition of trifluoroethanol (TFE), also promote hUb aggregation. The outcomes of this research have important implications for the prediction of physiological parameters that favor aggregate formation.

The Reaction Pathway of Cellulose Pyrolysis to a Multifunctional Chiral Building Block: The Role of Water Unveiled by a DFT Computational Investigation.

LAC (hydroxylactone (1R,5S)-1-hydroxy-3,6-dioxabicyclo[3.2.1]octan-2-one) is one of the most interesting products of the pyrolysis of cellulose and represents a useful chiral building block in organic synthesis. A computational investigation at the DFT level on the mechanism of formation of LAC shows that this species can be obtained following two reaction paths, path A and path B, starting from a well-known pyrolysis product (ascopyrone P). A series of internal rearrangements involving in all cases a proton transfer leads directly to LAC (path B). An alternative path (path A) can be also followed. From this path, via a "gate" connecting the two reaction channels, it is possible to reach path B and form LAC. In both cases, the rate-determining step of the process is the initial keto-enol isomerization. We found that water, which is present in the reaction mixture, "catalyzes" the reaction by assisting the proton transfers present in all the steps of the process. In particular, water lowers the barrier of the rate-determining step that becomes 40.9 kcal mol-1 (79.4 kcal mol-1 in the absence of water). The corresponding computed rate constant is 4.3×10 s-1 at 500 °C, a value which is consistent with the presence of LAC in the absence of metal catalysts. The results of this study on the non-catalyzed process underpin the important role played by water in the formation of pyrolysis products of cellulose where proton transfer is a key mechanistic step.

CNT-Confinement Effects on the Menshutkin SN2 Reaction: The Role of Nonbonded Interactions.

We investigated the effects of CNT confinement ((6,6) tube) on the model Menshutkin reaction H3N + H3CCl = H3NCH3((+)) + Cl((-)), which is representative of chemical processes involving developing of charge separation along the reaction pathway. We used either a full QM approach or a hybrid QM/MM approach. We found that the CNT significantly lowers the activation barrier with respect to the hypothetical gas-phase reaction: The activation barrier Ea varies from 34.6 to 25.7 kcal mol(-1) (a value similar to that found in a nonpolar solvent) and the endothermicity ΔE from 31.2 to 13.5 kcal mol(-1). A complex interplay between C-H···π, N-H···π, and Cl···π nonbonded interactions of the endohedral system with the CNT wall explains the lower barrier and lower endothermicity. The hybrid QM/MM approach (MM = UFF force field) does not reproduce satisfactorily the QM energy ΔE (18.1 vs 13.5 kcal mol(-1)), while optimum agreement is found in the barrier Ea (25.8 vs 25.7 kcal mol(-1)). These results suggest that the simple Qeq formalism (included in the MM potential) does not describe properly the effect of CNT polarization in the presence of the net charge separation featuring the final product. A more accurate estimate of the tube polarization was obtained with single-point QM/MM computations including PCM corrections (using the benzene dielectric constant) on the QM/MM optimized structures. After PCM corrections, Ea changes slightly (from 25.8 to 24.5 kcal mol(-1)), but a more significant variation is observed for ΔE that becomes 13.1 kcal mol(-1), in rather good agreement with the full QM. This level of theory (QM/MM with PCM correction, MM = UFF) represents a more general approach suitable for describing CNT-confined chemical processes involving significant charge separation. QM/MM computations were extended to CNTs of different radii: (4,4), (5,5), (7,7), (8,8), (9,9), (10,10), (12,12), (14,14) CNTs and, as a limit case, a graphene sheet. The lack of space available in the small tube (4,4) causes a strong structural distortion and a consequent increase in Ea and ΔE (40.8 and 44.0 kcal mol(-1), respectively). These quantities suddenly decrease with the augmented volume inside the (5,5) tube. For larger tubes, different structural arrangements of the endohedral system are possible, and Ea and ΔE remain almost constant until the limiting case of graphene.

Tuning Cysteine Reactivity and Sulfenic Acid Stability by Protein Microenvironment in Glyceraldehyde-3-Phosphate Dehydrogenases of Arabidopsis thaliana.

AIMS: Cysteines and H2O2 are fundamental players in redox signaling. Cysteine thiol deprotonation favors the reaction with H2O2 that generates sulfenic acids with dual electrophilic/nucleophilic nature. The protein microenvironment surrounding the target cysteine is believed to control whether sulfenic acid can be reversibly regulated by disulfide formation or irreversibly oxidized to sulfinates/sulfonates. In this study, we present experimental oxidation kinetics and a quantum mechanical/molecular mechanical (QM/MM) investigation to elucidate the reaction of H2O2 with glycolytic and photosynthetic glyceraldehyde-3-phosphate dehydrogenase from Arabidopsis thaliana (cytoplasmic AtGAPC1 and chloroplastic AtGAPA, respectively). RESULTS: Although AtGAPC1 and AtGAPA have almost identical 3D structure and similar acidity of their catalytic Cys149, AtGAPC1 is more sensitive to H2O2 and prone to irreversible oxidation than AtGAPA. As a result, sulfenic acid is more stable in AtGAPA. INNOVATION: Based on crystallographic structures of AtGAPC1 and AtGAPA, the reaction potential energy surface for Cys149 oxidation by H2O2 was calculated by QM. In both enzymes, sulfenic acid formation was characterized by a lower energy barrier than sulfinate formation, and sulfonate formation was prevented by very high energy barriers. Activation energies for both oxidation steps were lower in AtGAPC1 than AtGAPA, supporting the higher propensity of AtGAPC1 toward irreversible oxidation. CONCLUSIONS: QM/MM calculations coupled to fingerprinting analyses revealed that two Arg of AtGAPA (substituted by Gly and Val in AtGAPC1), located at 8-15 Å distance from Cys149, are the major factors responsible for sulfenic acid stability, underpinning the importance of long-distance polar interactions in tuning sulfenic acid stability in native protein microenvironments.

Gold(I)-Catalyzed Dearomative [2+2]-Cycloaddition of Indoles with Activated Allenes: A Combined Experimental-Computational Study.

The gold-catalyzed synthesis of methylidene 2,3-cyclobutane-indoles is documented through a combined experimental/computational investigation. Besides optimizing the racemic synthesis of the tricyclic indole compounds, the enantioselective variant is presented to its full extent. In particular, the scope of the reaction encompasses both aryloxyallenes and allenamides as electrophilic partners providing high yields and excellent stereochemical controls in the desired cycloadducts. The computational (DFT) investigation has fully elucidated the reaction mechanism providing clear evidence for a two-step reaction. Two parallel reaction pathways explain the regioisomeric products obtained under kinetic and thermodynamic conditions. In both cases, the dearomative CC bond-forming event turned out to be the rate-determining step.

Gold(I)-Assisted α-Allylation of Enals and Enones with Alcohols.

The intermolecular α-allylation of enals and enones occurs by the condensation of variously substituted allenamides with allylic alcohols. Cooperative catalysis by [Au(ItBu)NTf2] and AgNTf2 enables the synthesis of a range of densely functionalized α-allylated enals, enones, and acyl silanes in good yield under mild reaction conditions. DFT calculations support the role of an α-gold(I) enal/enone as the active nucleophilic species.