Mechanistic Study on Gold(I)-Catalyzed Unsaturated Spiroketalization Reaction

2022 ◽  
Vol 19 ◽  
Author(s):  
Kamlesh Sharma
Keyword(s):  
Activation Barrier ◽  
Ring Formation ◽  
Hydroxyl Group ◽  
Mechanistic Study ◽  
Protecting Group ◽  
Wide Range ◽  
Oxocarbenium Ion ◽  
Metal Catalyzed ◽  
Insight Into ◽  
Mechanism Of The Reaction

Abstract: The mechanism of metal-catalyzed spiroketalization of propargyl acetonide is explored by employing DFT with the B3LYP/6-31+G(d) method. Acetonide is used as a regioselective regulator in the formation of monounsaturated spiroketal. The energies of transition states, intermediates, reactants and products are calculated to provide new insight into the mechanism of the reaction. The energetic features, validation of the observed trends in regioselectivity are conferred in terms of electronic indices via FMO analysis. The presence of acetonide facilitates a stepwise spiroketalization as it masks the competing nucleophile, and thus hydroxyl group present, exclusively acts as a nucleophile. The vinyl gold intermediate 3 is formed from 2 via activation barrier TS1. This is the first ring formation, which is 6-exo-dig cyclization. The intermediate 3 is converted into allenyl ether 4, which isomerizes to the intermediate oxocarbenium ion 5 via activation barrier TS2. The intermediate 5 cyclizes to 6 via TS3. This is the second ring formation. The intermediate 6 on protodeauration turns into 6,6-monounsaturated spiroketal 7. It is concluded that acetonide as a protecting group serves the purpose, and thus a wide range of spiroketals can be prepared, regioselectivity.

Mechanistic study of methanol oxidation by RuIV–oxo complexes

2015 ◽  
Vol 19 (01-03) ◽  
pp. 417-426
Author(s):  
Yoshihito Shiota ◽  
Shoya Takahashi ◽  
Shingo Ohzu ◽  
Tomoya Ishizuka ◽  
Takahiko Kojima ◽  
...  
Keyword(s):  
Dft Calculations ◽  
Methanol Oxidation ◽  
Density Functional ◽  
Activation Barrier ◽  
Hydrogen Abstraction ◽  
Hydroxyl Group ◽  
Mechanistic Study ◽  
Activation Barriers ◽  
Bond Dissociation ◽  
Oxo Complexes

The catalytic conversion of methanol to formaldehyde by three kinds of non-porphyrin Ru complexes, Ru IV O ( TPA ) (TPA = tris(2-pyridylmethyl)amine) (1a), Ru IV O (6- COO - TPA ) (6-COO-TPA = 2-(6-carboxyl-pyridyl)methyl-bis(2-pyridylmethyl)amine) (1b), and Ru IV O ( N4Py ) (N4Py = N,N-bis(2-pyridyl-methyl)-N-bis(2-pyridyl)methylamine) (1c), is discussed by using density functional theory (DFT) calculations. There are two possible reaction pathways for the oxidation of methanol to formaldehyde with respect to the first hydrogen abstraction from the methyl group (path 1) and the hydroxyl group (path 2). Path 1 and path 2 involve the hydroxymethyl radical (• CH 2 OH ) and the methoxyl radical ( CH 3 O •), respectively, as an intermediate. DFT calculations demonstrate that the two pathways are energetically comparable in the reactions by the three Ru IV –oxo complexes. The reactions with 1a and 1c are initiated by the C – H bond dissociation with activation barriers of 22.2 and 21.4 kcal/mol, respectively, while the reaction with 1b is initiated by the O – H bond dissociation with an activation barrier of 18.1 kcal/mol. However, the calculations showed that the rate-determining step is the H -atom abstraction from the CH 3 group of methanol in all the pathways. These results are in good agreement with kinetic analysis of the reactions by the Ru IV –oxo complexes, being useful for considering the mechanism of methanol oxidation.

scholarly journals An Efficient Synthesis of Aryl-Substituted Pyrroles by the Suzuki–Miyaura Coupling Reaction of SEM-Protected Pyrroles

Molecules ◽  
2019 ◽  
Vol 24 (8) ◽  
pp. 1594 ◽  
Author(s):  
Keli Cui ◽  
Meng Gao ◽  
Hongyi Zhao ◽  
Dongfeng Zhang ◽  
Hong Yan ◽  
...  
Keyword(s):  
Coupling Reaction ◽  
Coupling Reactions ◽  
Protecting Group ◽  
Reaction Conditions ◽  
Cross Coupling Reactions ◽  
Wide Range ◽  
Synthetic Utility ◽  
Substituted Pyrroles ◽  
Metal Catalyzed ◽  
By Products

An efficient arylation of SEM-protected pyrroles by the Suzuki–Miyaura coupling reaction has been developed. The reaction can be carried out under mild conditions to provide aryl-substituted pyrroles in moderate to excellent yields. The scope and limitations of the methodology were evaluated, and the reaction was tolerant of a wide range of functionalities. Compared to the reported methods, the protocol has some advantages, such as commercially available materials, no debrominated by-products being formed, and the amine-protecting group being stable under the reaction conditions. The synthetic utility of the product has also been demonstrated, with several common transformations of the aryl-substituted pyrrole product being conducted. This protocol will offer the opportunity to explore other metal-catalyzed cross-coupling reactions employing SEM-protected pyrroles.

Sentence-Based Experience Logging in New Hearing Aid Users

2020 ◽  
Vol 29 (3S) ◽  
pp. 631-637
Author(s):  
Katja Lund ◽  
Rodrigo Ordoñez ◽  
Jens Bo Nielsen ◽  
Dorte Hammershøi
Keyword(s):  
Hearing Aid ◽  
Patient Experiences ◽  
Online Tool ◽  
Rehabilitation Process ◽  
Hearing Rehabilitation ◽  
Clinical Observations ◽  
Hearing Aid Use ◽  
Wide Range ◽  
Insight Into ◽  
Shed Light

Purpose The aim of this study was to develop a tool to gain insight into the daily experiences of new hearing aid users and to shed light on aspects of aided performance that may not be unveiled through standard questionnaires. Method The tool is developed based on clinical observations, patient experiences, expert involvement, and existing validated hearing rehabilitation questionnaires. Results An online tool for collecting data related to hearing aid use was developed. The tool is based on 453 prefabricated sentences representing experiences within 13 categories related to hearing aid use. Conclusions The tool has the potential to reflect a wide range of individual experiences with hearing aid use, including auditory and nonauditory aspects. These experiences may hold important knowledge for both the patient and the professional in the hearing rehabilitation process.

Monodentate Trialkylphosphines: Privileged Ligands in Metal-catalyzed Crosscoupling Reactions

2020 ◽  
Vol 24 (3) ◽  
pp. 231-264 ◽  
Author(s):  
Kevin H. Shaughnessy
Keyword(s):  
Transition Metal ◽  
Cross Coupling ◽  
Coupling Reactions ◽  
Cross Coupling Reactions ◽  
Aryl Bromides ◽  
Wide Range ◽  
Sterically Demanding ◽  
Transition Metal Catalyzed ◽  
Catalyzed Reactions ◽  
Metal Catalyzed

Phosphines are widely used ligands in transition metal-catalyzed reactions. Arylphosphines, such as triphenylphosphine, were among the first phosphines to show broad utility in catalysis. Beginning in the late 1990s, sterically demanding and electronrich trialkylphosphines began to receive attention as supporting ligands. These ligands were found to be particularly effective at promoting oxidative addition in cross-coupling of aryl halides. With electron-rich, sterically demanding ligands, such as tri-tertbutylphosphine, coupling of aryl bromides could be achieved at room temperature. More importantly, the less reactive, but more broadly available, aryl chlorides became accessible substrates. Tri-tert-butylphosphine has become a privileged ligand that has found application in a wide range of late transition-metal catalyzed coupling reactions. This success has led to the use of numerous monodentate trialkylphosphines in cross-coupling reactions. This review will discuss the general properties and features of monodentate trialkylphosphines and their application in cross-coupling reactions of C–X and C–H bonds.

scholarly journals Engineering the Interface between Inorganic Nanoparticles and Biological Systems through Ligand Design

Nanomaterials ◽  
2021 ◽  
Vol 11 (4) ◽  
pp. 1001
Author(s):  
Rui Huang ◽  
David C. Luther ◽  
Xianzhi Zhang ◽  
Aarohi Gupta ◽  
Samantha A. Tufts ◽  
...  
Keyword(s):  
Organic Synthesis ◽  
Molecular Design ◽  
Biological Systems ◽  
Ligand Design ◽  
Inorganic Nanoparticles ◽  
Organic Ligands ◽  
Biological Applications ◽  
Wide Range ◽  
Insight Into

Nanoparticles (NPs) provide multipurpose platforms for a wide range of biological applications. These applications are enabled through molecular design of surface coverages, modulating NP interactions with biosystems. In this review, we highlight approaches to functionalize nanoparticles with ”small” organic ligands (Mw < 1000), providing insight into how organic synthesis can be used to engineer NPs for nanobiology and nanomedicine.

scholarly journals Gas Damping in Capacitive MEMS Transducers in the Free Molecular Flow Regime

Sensors ◽  
2021 ◽  
Vol 21 (7) ◽  
pp. 2566
Author(s):  
Boris A. Boom ◽  
Alessandro Bertolini ◽  
Eric Hennes ◽  
Johannes F. J. van den Brand
Keyword(s):  
Flow Regime ◽  
Gas Diffusion ◽  
Diffusion Time ◽  
Molecular Flow ◽  
Free Molecular Flow ◽  
Simple Analytical Model ◽  
Gas Damping ◽  
Wide Range ◽  
Capacitive Mems ◽  
Insight Into

We present a novel analysis of gas damping in capacitive MEMS transducers that is based on a simple analytical model, assisted by Monte-Carlo simulations performed in Molflow+ to obtain an estimate for the geometry dependent gas diffusion time. This combination provides results with minimal computational expense and through freely available software, as well as insight into how the gas damping depends on the transducer geometry in the molecular flow regime. The results can be used to predict damping for arbitrary gas mixtures. The analysis was verified by experimental results for both air and helium atmospheres and matches these data to within 15% over a wide range of pressures.

scholarly journals Computational Design of Radical Recognition Assay with the Possible Application of Cyclopropyl Vinyl Sulfides as Tunable Sensors

2021 ◽  
Vol 22 (14) ◽  
pp. 7637
Author(s):  
Liliya T. Sahharova ◽  
Evgeniy G. Gordeev ◽  
Dmitry B. Eremin ◽  
Valentine P. Ananikov
Keyword(s):  
Uv Light ◽  
Computational Design ◽  
Energy Profiles ◽  
Vinyl Sulfides ◽  
Tunable Sensors ◽  
Radical Generation ◽  
Metal Catalyzed ◽  
Dynamics Simulations ◽  
Simulations And Modeling ◽  
Insight Into

The processes involving the capture of free radicals were explored by performing DFT molecular dynamics simulations and modeling of reaction energy profiles. We describe the idea of a radical recognition assay, where not only the presence of a radical but also the nature/reactivity of a radical may be assessed. The idea is to utilize a set of radical-sensitive molecules as tunable sensors, followed by insight into the studied radical species based on the observed reactivity/selectivity. We utilize this approach for selective recognition of common radicals—alkyl, phenyl, and iodine. By matching quantum chemical calculations with experimental data, we show that components of a system react differently with the studied radicals. Possible radical generation processes were studied involving model reactions under UV light and metal-catalyzed conditions.

scholarly journals Prediction of Dead Oil Viscosity: Machine Learning vs. Classical Correlations

Energies ◽  
2021 ◽  
Vol 14 (4) ◽  
pp. 930
Author(s):  
Fahimeh Hadavimoghaddam ◽  
Mehdi Ostadhassan ◽  
Ehsan Heidaryan ◽  
Mohammad Ali Sadri ◽  
Inna Chapanova ◽  
...  
Keyword(s):  
Machine Learning ◽  
Viscosity Data ◽  
Oil Viscosity ◽  
Pvt Data ◽  
Proposed Model ◽  
Wide Range ◽  
Engineering Problems ◽  
Functional Forms ◽  
Insight Into

Dead oil viscosity is a critical parameter to solve numerous reservoir engineering problems and one of the most unreliable properties to predict with classical black oil correlations. Determination of dead oil viscosity by experiments is expensive and time-consuming, which means developing an accurate and quick prediction model is required. This paper implements six machine learning models: random forest (RF), lightgbm, XGBoost, multilayer perceptron (MLP) neural network, stochastic real-valued (SRV) and SuperLearner to predict dead oil viscosity. More than 2000 pressure–volume–temperature (PVT) data were used for developing and testing these models. A huge range of viscosity data were used, from light intermediate to heavy oil. In this study, we give insight into the performance of different functional forms that have been used in the literature to formulate dead oil viscosity. The results show that the functional form f(γAPI,T), has the best performance, and additional correlating parameters might be unnecessary. Furthermore, SuperLearner outperformed other machine learning (ML) algorithms as well as common correlations that are based on the metric analysis. The SuperLearner model can potentially replace the empirical models for viscosity predictions on a wide range of viscosities (any oil type). Ultimately, the proposed model is capable of simulating the true physical trend of the dead oil viscosity with variations of oil API gravity, temperature and shear rate.

A new species of Sclerocephalus with a fully ossified endocranium gives insight into braincase evolution in temnospondyls

2021 ◽  
pp. 1-13
Author(s):  
Rainer R. Schoch ◽  
Gabriela Sobral
Keyword(s):  
New Species ◽  
Character Evolution ◽  
Late Paleozoic ◽  
New Taxon ◽  
Early Permian ◽  
Top Predator ◽  
Central European ◽  
Wide Range ◽  
A New Species ◽  
Insight Into

Abstract The late Paleozoic temnospondyl Sclerocephalus formed an aquatic top predator in various central European lakes of the late Carboniferous and early Permian. Despite hundreds of specimens spanning a wide range of sizes, knowledge of the endocranium (braincase and palatoquadrate) remained very insufficient in Sclerocephalus and other stereospondylomorphs because even large skulls had unossified endocrania. A new specimen from a stratigraphically ancient deposit at St. Wendel in southwestern Germany is recognized as representing a new taxon, S. concordiae new species, and reveals a completely ossified endocranium. The sphenethmoid was completely ossified from the basisphenoid to the anterior ethmoid region, co-ossified with the parasphenoid, and the basipterygoid joint was fully established. The pterygoid bears a slender, S-shaped epipterygoid, which formed a robust pillar lateral to the braincase. The massive stapes was firmly sutured to the parasphenoid. In the temnospondyl endocranium, character evolution involved various changes in the epipterygoid region, which evolved distinct morphologies in each of the major clades. UUID: http://zoobank.org/5e6d2078-eacf-4467-84cf-a12efcae7c0b

scholarly journals An Insight into Saponins from Quinoa (Chenopodium quinoa Willd): A Review

Molecules ◽  
2020 ◽  
Vol 25 (5) ◽  
pp. 1059 ◽  
Author(s):  
Khadija El Hazzam ◽  
Jawhar Hafsa ◽  
Mansour Sobeh ◽  
Manal Mhada ◽  
Moha Taourirte ◽  
...  
Keyword(s):  
Heat Treatment ◽  
Bitter Taste ◽  
Biological Activities ◽  
Chenopodium Quinoa ◽  
Toxic Effects ◽  
Mechanical Abrasion ◽  
Important Group ◽  
The Past ◽  
Wide Range ◽  
Insight Into

Saponins are an important group found in Chenopodium quinoa. They represent an obstacle for the use of quinoa as food for humans and animal feeds because of their bitter taste and toxic effects, which necessitates their elimination. Several saponins elimination methods have been examined to leach the saponins from the quinoa seeds; the wet technique remains the most used at both laboratory and industrial levels. Dry methods (heat treatment, extrusion, roasting, or mechanical abrasion) and genetic methods have also been evaluated. The extraction of quinoa saponins can be carried out by several methods; conventional technologies such as maceration and Soxhlet are the most utilized methods. However, recent research has focused on technologies to improve the efficiency of extraction. At least 40 saponin structures from quinoa have been isolated in the past 30 years, the derived molecular entities essentially being phytolaccagenic, oleanolic and serjanic acids, hederagenin, 3β,23,30 trihydroxy olean-12-en-28-oic acid, 3β-hydroxy-27-oxo-olean-12en-28-oic acid, and 3β,23,30 trihydroxy olean-12-en-28-oic acid. These metabolites exhibit a wide range of biological activities, such as molluscicidal, antifungal, anti-inflammatory, hemolytic, and cytotoxic properties.

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