Abstract: A bisbenzamidine DNA binding agent can be easily dimerized by alkylation of its terminal amidine groups to afford an extended minor groove binder with over 20-fold enhanced DNA affinity towards extended A/T-rich sites. NMR experiments in combination with molecular dynamics simulation studies provide structural insight into the insertion of this compound in the DNA minor groove, and antimicrobial assays demonstrate that the increased affinity translates into higher antileishmanial activity.

External link: https://academic.oup.com/narmolmed/advance-article/doi/10.1093/narmme/ugae022/7917611?login=true

We are so pleased to announce here that our last paper at Org. Lett., entitled "Assembly of 2-Substituted Tetrahydroquinolines from ortho-Methylbenzenesulfamides and Dienes, Using a C(sp3)–H Activation/Annulation Sequence" and authored by I. Huertas-Morales, B. Cendón, D. Costa, J. L. Mascareñas and M. Gulías, has been accepted and it's already on-line.

Abstract: 1,2,3,4-Tetrahydroquinolines (THQs) are essential structural cores in many natural products and pharmaceutical drugs. Especially relevant are those presenting substitutions at position 2, yet practical methods for their one-step assembly from acyclic precursors are very scarce. Herein, we present a straightforward approach to assembling these skeletons from ortho-methylanilines using a palladium-catalyzed C(sp3)–H activation/formal cycloaddition sequence. Key for the success of the approach is the use of dienes as partners, since they lead to stable π–allyl palladium intermediates that prevent β-hydride elimination processes and allow installation of versatile alkenyl handles at position 2. Moreover, installing a perfluorobenzenesulfonyl substituent at the amine not only facilitates the C–H activation but also allows for an easy recovery of the free amine.

External link: https://pubs.acs.org/doi/10.1021/acs.orglett.4c02292

Abstract: The combination of a Pd(0) source and a phosphoramidite ligand promotes a formal allylic cross-coupling between alkylidenecyclopropanes (ACPs) and boronic acids to yield synthetically appealing 1,1-disubstituted alkenes. Remarkably, the reaction proceeds both under neutral and basic conditions, and works with both aryl- and alkenylboronic acids. DFT calculations suggest that the reaction entails a C-C activation/protonation mechanism instead of a hydropalladation pathway, such as has been proposed for other metal-promoted hydrofunctionalizations of ACPs.

External link: https://onlinelibrary.wiley.com/doi/abs/10.1002/adsc.202400657

We are so pleased to announce here that our last minireview at Angew. Chem. Int Ed., entitled "Bioorthogonal Synthetic Chemistry Enabled by Visible-Light Photocatalysis" and authored by M. Mato, X. Fernández-González, C. D'Avino, M. Tomás-Gamasa and J. L. Mascareñas, has been accepted and it's already on-line (gold Open Access).

Abstract: The field of bioorthogonal chemistry has revolutionized our ability to interrogate and manipulate biological systems at the molecular level. However, the range of chemical reactions that can operate efficiently in biological environments without interfering with the native cellular machinery, remains limited. In this context, the rapidly growing area of photocatalysis offers a promising avenue for developing new type of bioorthogonal tools. The inherent mildness, tunability, chemoselectivity, and external controllability of photocatalytic transformations make them particularly suitable for applications in biological and living systems. This minireview summarizes recent advances in bioorthogonal photocatalytic technologies, with a particular focus on their potential to enable the selective generation of designed products within biologically relevant or living settings.

External link: https://onlinelibrary.wiley.com/doi/10.1002/anie.202413506