34 research outputs found
Anti-hydroarylation of activated internal alkynes: merging pd and energy transfer catalysis
A general catalytic anti-hydroarylation of electron-deficient internal alkynes compatible with both electron-poor and electron-rich aryl reagents is reported. This selectivity is achieved through a sequential syn-carbopalladation of the alkyne by an Ar-Pd species, followed by a tandem, Ir-photocatalyzed, counter-thermodynamic E → Z isomerization. The use of ortho-substituted boronic acids enables direct access to pharmaceutically relevant heterocyclic cores via a cascade process. Mechanistic insight into the involvement of Ar-Pd versus Pd-H as an active species is providedWe thank the Ministerio de Economía, Industria y Competitividad (CTQ2015-66954-P, MINECO/FEDER, UE and FEDER/Ministerio de Ciencia, Innovación y Universidades- ́ Agencia Estatal de Investigación/Proyecto PGC2018-098660- ́ B-I00) for financial suppor
Transition-metal-catalyzed functionalization of alkynes with organoboron reagents: new trends, nechanistic insights, and applications
Catalytic functionalization of alkynes with organoboron reagents provides a straightforward access to stereochemically defined multisubstituted alkenes, which are structural motifs commonly found in bioactive compounds and organic materials. Recent progress has substantially broadened the scope of this field on several fronts. Strategies for regioselectivity control in the 1,2-migratory insertion across unsymmetrical internal alkynes, as well as for the direct access to products with anti-insertion stereochemistry, have been devised. The alkenyl-to-aryl 1,4-metal migration upon metal insertion has been recently exploited in powerful cascade sequences leading to complex polycyclic scaffolds, including the development of enantioselective processes. Elegant enantiospecific and dynamic kinetic resolution methods have been developed for accessing chiral allenes from propargylic alcohol derivatives. Mechanistic manifolds have emerged based on single-electron transfer (SET) that have provided a fresh impetus for alkyne 1,2-difunctionalization with complementary stereoselectivity to processes relying on 1,2-insertion of R-M species. Herein, we discuss the most recent advances in transition-metal-catalyzed functionalization of alkynes using organoboron reagents, categorized according to the type of mechanistic outcome. Emphasis is placed on mechanistic aspects, synthetic utility, limitations, and challenges for future researchWe thank the Ministerio de Ciencia e Innovación (MICINN) and Fondo Europeo de Desarrollo Regional (FEDER, UE) for financial support (Agencia Estatal de Investigación/Project PGC2018-098660-B-I00). J.C. thanks the Ministerio de Educación, Cultura y Deporte (MECD), for an FPU fellowship. Inés Manjón is gratefully acknowledged for her assistance with the final edition of the manuscrip
Cu-Catalyzed Silylation of Alkynes: A Traceless 2-Pyridylsulfonyl Controller Allows Access to either Regioisomer on Demand
This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of the American Chemical Society, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://pubs.acs.org/doi/abs/10.1021/jacs.5b02667The Cu-catalyzed silylation of terminal and internal alkynes bearing a 2-pyridyl sulfonyl group (SO2Py) at the propar-gylic position affords a breadth of vinyl silanes in good yields and excellent regio- and stereocontrol under mild conditions. The directing SO2Py group is essential in terms of reaction efficiency and chemoselectivity. Importantly, this group also provides the ability to reverse the regiochemical outcome of the reaction, opening the access to either regioisomer without modification of the starting substrate by virtue of an in situ base-promoted alkyne to allene equilibration which takes place prior to the silylcupration process. Furthermore, removal of the directing SO2Py allows for further elaboration of the silylation products. In particular, a one-pot tandem alkyne silylation/allylic substitution sequence, in which both steps are catalyzed by the same Cu species, opens up a new approach for the access to either formal hydrosilylation regioisomer of unsymmetrical aliphatic-substituted internal alkynes from propargyl sulfonesThis work was supported by the Ministerio de Economía y Com-petitividad (MINECO, CTQ2012-35790) and the European Union for a Marie Curie Career Integration Grant (to P.M). J. R. and P.M. thank MINECO for a FPI predoctoral fellowship and a Ramón y Cajal contract, respectivel
Beyond classical sulfone chemistry: metal- and photocatalytic approaches for C-S bond functionalization of sulfones
The exceptional versatility of sulfones has been extensively exploited in organic synthesis across several decades. Since the first demonstration in 2005 that sulfones can participate in Pd-catalysed Suzuki-Miyaura type reactions, tremendous advances in catalytic desulfitative functionalizations have opened a new area of research with burgeoning activity in recent years. This emerging field is displaying sulfone derivatives as a new class of substrates enabling catalytic C-C and C-X bond construction. In this review, we will discuss new facets of sulfone reactivity toward further expanding the flexibility of C-S bonds, with an emphasis on key mechanistic features. The inherent challenges confronting the development of these strategies will be presented, along with the potential application of this chemistry for the synthesis of natural products. Taken together, this knowledge should stimulate impactful improvements on the use of sulfones in catalytic desulfitative C-C and C-X bond formation. A main goal of this article is to bring this technology to the mainstream catalysis practice and to serve as inspiration for new perspectives in catalytic transformation
The Acidity of a Carbon Nucleophile Dictates Enantioselectivity and Reactivity in Michael Additions to Aromatic and Aliphatic Enals via Iminium Activation
The Michael addition of activated methylenes to β-substituted α,β-unsaturated aldehydes (enals) via iminium catalysis takes place following reactivity and enantioselectivity patterns which depend on the electronic nature of the substituent in the β position (β-aryl or β-alkyl). Application of the same reaction conditions to both families of enals may result in erratic levels of asymmetric induction in the reactions of β-aryl enals or low reactivity with β-alkyl enals. A systematic analysis of this behavior using phenylacetic acid derivatives as case studies has led us to find a general trend: the different problems found for β-aryl and β-alkyl enals depend on the acidity of the nucleophile, and the outcome of the reaction for both types of enals can be improved substantially by careful choice of catalyst, solvent, and additive. Furthermore, this study has allowed us to understand subtle aspects of this transformation and has enabled the formulation of a general and reliable protocol to obtain high yields and enantioselectivities consistently, regardless of the acidity of the nucleophile and the nature of the substituent (aromatic or aliphatic) at the β positionWe thank CTQ-2009-12168, CAM (AVANCAT CS2009/PPQ-1634), UAM-CAM (CCG10-UAM/PPQ-5769), CTQ-2012-35957, CTQ2015-63997-C2-1-P, CTQ2016-78779-R and FOTOCARBON-CAM S2013/MIT-2841 for financial support. S.D. thanks the Comunidad Autónoma de Madrid (CAM), and E.R. and S.M. thank MICINN, for predoctoral fellowships. P.M. thanks MICINN for a Ramón y Cajal contract and the EU for a Marie Curie grant (CIG: HYPERCAT-30422
DFT calculation, a practical tool to predict the electrochemical behaviour of organic electrolytes in aqueous redox flow batteries
Herein, a computational predictive tool for redox flow batteries based on NBO and ADCH charge distribution
studies is presented and supported by experimental evidence. Using highly water soluble (>2 M) non-planar 2,2′
-
bipyridinium salts as a case of study, this work presents a DFT protocol that successfully predicts the stability and
forecasts their potential application as active materials for Aqueous Organic Redox Flow Batteries (AORFB). An
initial theoretical-experimental characterization of selected bipyridines served to determine the effect of the ring
size, geometry, and electron density on the physico-chemical properties of the materials. Nonetheless, the NBO
and ADCH charge analyses were essential tools to understand the stability of the reduced species in terms of
electronic delocalization and the importance of the molecular design on the stability of electrolyte for AORFB.
Based on these results, the cell performance of seven-membered 2,2′
-bypiridinium salt, (2), and m-Me substituted homologous, (4), were compared. The significantly lower capacity decay rendered by compound 4 based electrolyte, (0.35%/cycle) compared with compound 2 based electrolyte, (0.71%/cycle) was in good agreement with the predicted stability. The aim of this work is to highlight the powerful synergy between DFT calculations and organic chemistry in predicting the behaviour of different negolytesThis work has been funded by the European Union under the
HIGREEW project, Affordable High-performance Green Redox Flow
batteries (Grant agreement no. 875613). H2020: LC-BAT-4-2019. A.C.
Lopes acknowledges the Ramon y Cajal (RYC2021-032277-I) research
fellowship, the financial support from Ministerio de Ciencia e
Innovacion ´ / AEI /10.13039/501100011033 and from European Union
NextGenerationEU/PRTR. We also thank the CCC-UAM (Graforr project) for allocation of computer tim
Design of New Dispersants Using Machine Learning and Visual Analytics
Artificial intelligence (AI) is an emerging technology that is revolutionizing the discovery of new materials. One key application of AI is virtual screening of chemical libraries, which enables the accelerated discovery of materials with desired properties. In this study, we developed computational models to predict the dispersancy efficiency of oil and lubricant additives, a critical property in their design that can be estimated through a quantity named blotter spot. We propose a comprehensive approach that combines machine learning techniques with visual analytics strategies in an interactive tool that supports domain experts’ decision-making. We evaluated the proposed models quantitatively and illustrated their benefits through a case study. Specifically, we analyzed a series of virtual polyisobutylene succinimide (PIBSI) molecules derived from a known reference substrate. Our best-performing probabilistic model was Bayesian Additive Regression Trees (BART), which achieved a mean absolute error of (Formula presented.) and a root mean square error of (Formula presented.), as estimated through 5-fold cross-validation. To facilitate future research, we have made the dataset, including the potential dispersants used for modeling, publicly available. Our approach can help accelerate the discovery of new oil and lubricant additives, and our interactive tool can aid domain experts in making informed decisions based on blotter spot and other key propertie
Iterative dual-metal and energy transfer catalysis enables stereodivergence in alkyne difunctionalization: Carboboration as case study
Stereochemically defined tetrasubstituted olefins are widespread structural elements of organic molecules and key intermediates in organic synthesis. However, flexible methods enabling stereodivergent access to E and Z isomers of fully substituted alkenes from a common precursor represent a significant challenge and are actively sought after in catalysis, especially those amenable to complex multifunctional molecules. Herein, we demonstrate that iterative dual-metal and energy transfer catalysis constitutes a unique platform for achieving stereodivergence in the difunctionalization of internal alkynes. The utility of this approach is showcased by the stereodivergent synthesis of both stereoisomers of tetrasubstituted β-boryl acrylates from internal alkynoates with excellent stereocontrol via sequential carboboration and photoisomerization. The reluctance of electron-deficient internal alkynes to undergo catalytic carboboration has been overcome through cooperative Cu/Pd-catalysis, whereas an Ir complex was identified as a versatile sensitizer that is able to photoisomerize the resulting sterically crowded alkenes. Mechanistic studies by means of quantum-chemical calculations, quenching experiments, and transient absorption spectroscopy have been applied to unveil the mechanism of both stepsPGC2018-098660−B-I00, Horizon2020 (ERC) No.648319, PID2019-106315RB-I00, PID2020-118593RB-C22
San Adrian: un nuevo yacimiento de la Edad del Bronce en el Norte de la Peninsula Iberica
Bronze Age studies carried out in the Cantabrian Region have traditionally focused on prestige goods and funerary contexts. As a result of this, the lack of information about daily activities, subsistence strategies, and human settlement on a regional scale is evident in the state of art. However, current research has achieved new discoveries in recent years, allowing a reconstruction of some aspects of the economic structure, settlements, material culture and the palaeoenvironment during the Bronze Age. Indeed, besides the funerary practices discovered in 1983 in San Adrian (Parztuergo Nagusia, Gipuzkoa), research has now revealed the presence of Upper Palaeolithic and Early Bronze Age occupations. This paper presents a first characterization of the retrieved evidence and a preliminary evaluation of the archaeological site and its environment. San Adrian is a tunnel-shaped cave located at 1,000 meters a.s.l. in the Aizkorri mountain range, opening a passage beneath the Atlantic-Mediterranean watershed in northern Iberia. The strategic character of this mountain site is demonstrated by the presence of Upper Palaeolithic and Bronze Age occupations, and by the construction of a road passing through it and the fortification of both its entrances in the Middle Ages. The aim of the archaeological survey started in 2008 was to identify, describe and evaluate the heritage potential of the cave, because previous fieldwork had only managed to make surface finds in the side galleries, including a medieval hoard and Bronze Age human remains. The work carried out by our research group at San Adrian includes a series of test pits and the excavation of an area nine square metres in size following stratigraphic criteria. In the current state, we identified at least two contexts corresponding to Late Upper Palaeolithic and Bronze Age occupations in the cave. Fieldwork included the sieving and flotation of sediment and the collection of samples for different types of analysis: palynology, carpology, sedimentology, and radiocarbon dating. The evidence is being studied by a multidisciplinary team according to expertise requirements for each topic: palaeobotany and environment, archaeozoology, sedimentology, geology, physical anthropology, prehistoric industries (lithics, pottery and bone) and archaeological and historical documentation. Because of its recent discovery, Upper Palaeolithic evidence remains still under study, but first results on Bronze Age layers can be presented. The ongoing archaeobotanical and archaeozoological studies reveal the exploitation of domestic plants and fauna complemented by hunting and foraging of wild species. At the same time, the archaeological artefacts and their production sequences show the exploitation of nearby resources on both sides of the mountain range, while prestige goods are absent. This evidence is also used to estimate the regularity of cave occupations and to propose a model of seasonal exploitation of the mountain environment. The results obtained reveal the exploitation of resources from both the Mediterranean and Atlantic basins, and contribute towards an understanding of the daily activities of Bronze Age societies. In addition, the evidence shows the exchange and circulation of quotidian products between the Cantabrian region and inland Iberia in other networks than those of prestige goods