Please find below all relevant news regarding our Group.
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Abstract:We report an Ir(I)-catalyzed cycloisomerization methodology that provides access to carbocyclic systems bearing exo-alkene moieties from alkynyl-equipped acyclic precursors. The method relies on the C-H activation of olefinic and (het-ero)aromatic C(sp2)–H bonds, followed by an exo-cyclization to a tethered alkyne, and provides interesting cyclic diene products that are amenable of further elaboration. Importantly, DFT calculations suggests that, in contrast to related hydrocarbonations of alkenes in which either migratory insertions or C-C reductive eliminations have been suggested to be rate determining, in our reac-tions, the energetic barrier of these steps is lower than that of the previous C–H activation.
External link: https://pubs.acs.org/doi/abs/10.1021%2Facscatal.8b02139
"Intracellular deprotection reactions mediated by palladium complexes equipped with designed phosphine ligands", authored by M. Martínez-Calvo, J. R. Couceiro, P. Destito, J. Rodriguez, J. Mosquera and J. L. Mascareñas, is our latest paper at ACS Catalysis.
Abstract:Discrete palladium (II) complexes featuring purposely designed phosphine ligands can promote depropargylation and deallylation reactions in cell lysates. The performance of these complexes is superior to that of other palladium sources, which apparently are rapidly deactivated in such hostile complex media. This good balance between reactiv-ity and stability allows the use of these discrete phosphine palladium complexes in living mammalian cells, whereby they can mediate similar transformations. The presence of a phosphine ligand in the coordination sphere of palladi-um also provides for the introduction of targeting groups, such as hydrophobic phosphonium moieties, which facili-tate the accumulation of the complexes in mitochondria.
External link: https://pubs.acs.org/doi/10.1021/acscatal.8b01606
ABSTRACT: We report a highly enantioselective [3C + 2C] intramolecular cycloaddition of alkylidenecyclopropanes (ACPs) and alkenes. The best results are obtained by using sterically demanding chiral phosphoramidite ligands derived from Vapol. Moreover, we also show that related, but less bulky, phosphoramidites can also lead to very effective [4C + 3C] cycloadditions when dienes, instead of alkenes, are used as reacting partners. The reactions provide a practical, simple, and selective access to optically active, synthetically appealing 5,5- and 5,7-bicyclic systems.
External link: https://pubs.acs.org/doi/10.1021/acscatal.8b01296
We are very glad to announce the publication of our latest paper at Nature Communication, entitled "Concurrent and orthogonal gold(I) and ruthenium(II) catalysis inside living cells", by C. Vidal, M. Tomás-Gamasa, P. Destito, F. López and J. L. Mascareñas.
In which, we report a gold-mediated C–C bond formation that occurs in complex aqueous habitats, and demonstrate that the reaction can be translated to living mammalian cells.
See more at: https://www.usc.es/ciqus/es/noticias/alquimistasmediocelular
External link: https://www.nature.com/articles/s41467-018-04314-5
"Rhodium(III)‐Catalyzed Annulation of 2‐Alkenylanilides with Alkynes via C‐H Activation: a Direct Access to 2‐substituted Indolines" by Font, M., Cendón, B., Seoane, A., Mascareñas, J.L., and Gulías, M., is our recent communication to Angewandte Chemie International Edition
A Rh(III) complex featuring an electron‐deficient η5‐cyclopentadienyl ligand catalyzes an unusual annulation between alkynes and 2‐alkenylanilides, to form synthetically appealing 2‐substituted indolines. Formally, the process can be viewed as an allylic amination with concomitant hydrocarbonation of the alkyne. Mechanistic experiments indicate that this transformation involves a peculiar Rhodium migration with a concomitant 1,5‐H shift.
on the 3rd of May at Pazo de Vista Alegre (Ponte Ulla, A Coruña), the
annual meeting of our research group was a success. This was a one-day
meeting in which we shared ideas and proposals for future
research. Due to the fruitful discussion and debate, during six relaxed
and informal sessions, some new proposals will start to be developed in
the next weeks. Thanks to Pazo de Vista Alegre for being such nice
The group has just published an article at Chem. Sci
entitled "DNA-binding miniproteins based on zinc fingers. Assessment of the interaction using nanopores"
External link: http://dx.doi.org/10.1039/C7SC05441F
Noelia Casanova left the group and she joined the University of Cambridge (UK) with Dr. Robert Phipps.
Good luck Noelia!