Mauro Mato

Unmasking aryl thianthrenium salts in cells - Nature Synthesis Nature Synthesis - Unmasking aryl thianthrenium salts in cells

Research Highlight now online:

Unmasking aryl thianthrenium salts in cells by Thomas West

www.nature.com/articles/s44... ($)

Highlighting the @jacs.acspublications.org article by María Tomás-Gamasa, José L. Mascareñas and co-workers
#Chemsky

Photoredox Unmasking of Aromatic C–H Bonds in Living Environments Enabled by Thianthrenium Salts Prodrug strategies traditionally rely on masking polar functional groups of bioactive molecules with protecting units that can be removed by specific stimuli in biological settings. Here, we introduce an alternative uncaging approach that bypasses the need for heteroatom handles, based on reversible masking of aromatic C–H bonds with thianthrenium groups. Unmasking is triggered by low-energy photoredox activation, which generates aryl radicals that are rapidly reduced by endogenous bioreductants to restore the native C–H bond. Beyond establishing the feasibility of photoredox radical chemistry in living cells, we demonstrate a proof-of-concept application of this strategy for the modulation of activity of antifungal agents.

#CiQUS researchers have just published a JACS communication reporting an unconventional strategy to uncage drugs in live settings, based on a photoredox unmasking of aromatic C–H bonds

Congratulations to the authors on this outstanding work!

pubs.acs.org/doi/10.1021/...

#FondosEuropeos #RedeCIGUS

Red-Light Photoredox C–H Alkylation Enabled by Catalytic NADH, now out in @chemrxivbot.bsky.social

chemrxiv.org/doi/full/10....

From synthetic application to TAS mechanistic understanding, passing through radical biocompatibility.

Awesome collab @ciqus.bsky.social and @cadralab.bsky.social

Very glad to finally share this one, my project at @ciqus.bsky.social during my initial postdoc period, culminated through an outstanding bio collab with
Adrián and Alba from MetBioCat. Congrats all!!

We combine the power of C–H activation + red-light photoredox catalysis to unlock a new prodrug logic, based on the masking/unmasking of C–H bonds, which is operative in living contexts.

Photoredox Unmasking of Aromatic C–H Bonds in Living Environments Enabled by Thianthrenium Salts Prodrug strategies traditionally rely on masking polar functional groups of bioactive molecules with protecting units that can be removed by specific stimuli in biological settings. Here, we introduce...

Ever thought of designing prodrugs based on the protection of C–H bonds?

Now out in @jacs.acspublications.org
Photoredox Unmasking of Aromatic C–H Bonds in Living Environments Enabled by Thianthrenium Salts

pubs.acs.org/doi/10.1021/...

@ciqus.bsky.social

Very glad to finally share this one, my project at
@ciqus.bsky.social during my initial postdoc period, culminated through an outstanding bio collab with Adrián and Alba from MetBioCat. Congrats all!!

We combine the power of C–H activation + red-light photoredox catalysis to unlock a new prodrug logic, based on the masking/unmasking of C–H bonds, which is operative in living contexts.

Red-shifted photoredox generation and trapping of alkyl radicals towards bioorthogonality The photocatalytic generation and trapping of alkyl radicals is a powerful synthetic tool in organic chemistry, but it remains underexplored in biological settings. Here, we present two photoredox…

🔓Don't miss #OpenAccess research in our New Talent collection from María Tomás-Gamasa, José L. Mascareñas, @mauromato.bsky.social & co. at @ciqus.bsky.social describing the red-shifted photoredox generation & trapping of alkyl radicals towards bioorthogonality #orgchem

Congrats to Elliott, @hls111.bsky.social, Olivera, Patrick, Alexander and Daniel! Ligand Design Enables the Palladium-Catalyzed Intermolecular Carbochlorocarbonylation of Alkynes and Cyclopentenone Formation @jacs.acspublications.org pubs.acs.org/doi/full/10....

And spellcheck, please!

Breaking Kasha’s Rule to Enable Higher Reactivity in Photoredox Catalysis Nearly all photochemical transformations known to date follow Kasha’s rule, implying that reactions occur only from the lowest electronically excited state of a given spin multiplicity due to the fast...

We show how photoredox catalysis can bypass Kasha’s rule, enabling reactions from higher excited states.

This work, led by the exceptional @bjoernpfund.bsky.social, offers new insights into photochemical reactivity.

Published in JACS @jacs.acspublications.org

bit.ly/3IysmjX

Today in @science.org, @mikusp.bsky.social reports a method to replace the C2 of pyridines with N, affording pyridazines.

The change from electronically consonant (pyridine) to dissonant (pyridazine) opens retrosyntheses not typically available to the latter.

www.science.org/doi/10.1126/...

This time we answered this question👇️Thanks to all the team members and 4 unanonymous reviewers!
Please come to talk with me at poster B64 if you are @eucomc2025.bsky.social
#eucomc2025

www.nature.com/articles/s41...

How do you turn a carbonyl into sulfur?

In this work, Zining from our lab developed a carbonyl-to-sulfur swap enabled by a rationally designed N′-alkyl-hydrazonamide (NAHA) reagent that promotes double C-C bond activation.

www.science.org/doi/10.1126/...

José Luis Mascareñas, Premio Rei Jaume I en Investigación Básica El investigador del Centro Singular de Investigación en Química Biológica y Materiales Moleculares (CiQUS) y catedrático de la Universidade de Santiago de Compostela (USC), José Luis Mascareñas Cid,

🎖 𝗝𝗼𝘀é 𝗟𝘂𝗶𝘀 𝗠𝗮𝘀𝗰𝗮𝗿𝗲ñ𝗮𝘀, 𝗣𝗿𝗲𝗺𝗶𝗼 𝗥𝗲𝗶 𝗝𝗮𝘂𝗺𝗲 𝗜 2025 𝗲𝗻 𝗜𝗻𝘃𝗲𝘀𝘁𝗶𝗴𝗮𝗰𝗶ó𝗻 𝗕á𝘀𝗶𝗰𝗮

El investigador del CiQUS José Luis Mascareñas ha sido distinguido con uno de los galardones científicos más prestigiosos del país por sus trabajos en 𝗹𝗮 𝗳𝗿𝗼𝗻𝘁𝗲𝗿𝗮 𝗲𝗻𝘁𝗿𝗲 𝗹𝗮 𝗾𝘂í𝗺𝗶𝗰𝗮 𝗼𝗿𝗴𝗮𝗻𝗼𝗺𝗲𝘁á𝗹𝗶𝗰𝗮 𝘆 𝗹𝗮 𝗯𝗶𝗼𝗹𝗼𝗴í𝗮 𝗰𝗲𝗹𝘂𝗹𝗮𝗿.

How can Le Chatelier drive kinetics? @stefanborsley.bsky.social and I analyse Denton's organocatalytic Mitsunobu reaction and show water removal improvements outperform catalyst redesigns. Why? Removing water part way through the reaction resets the potential energy surface! doi.org/10.1021/jacs...

Rapid Access to Conjugated Z,Z,Z‐Trienes Z,Z,Z-triene: A novel method to facilitate rapid access to the otherwise inaccessible conjugated Z,Z,Z-triene motif is reported.

Hot off the press: Check out our report on a procedure to rapidly access Z,Z,Z-conjugated trienes @angewandtechemie.bsky.social: doi.org/10.1002/anie...

Preassembly‐Controlled Radical Recombination at Bismuth: Decarboxylative C─N Coupling with Sulfonamides Radical processes involving bismuth hold great potential, but innovative strategies are required to control the reactivity of bismuth intermediates. Herein, we report a direct photochemical decarboxy...

We expanded our Bismuth LMCT methodology towards the direct decarboxylative C-N coupling of carboxylic acids with sulfonamides - great work by Elina and Dominik now out in #Chem.Eur.J. #ChemSky 🧪
doi.org/10.1002/chem...

🚨Out now! Red-shifted activation and coupling of RAEs using NADH as bio-reductant.
First steps towards integrating alkyl radical chemistry in biological settings. Huge effort by David and Uxía! @ciqus.bsky.social
Thanks @orgbiomolchem.rsc.org for the invitation!

pubs.rsc.org/en/content/a...

If you're interested in a break from the doom-and-gloom, may I recommend our article, online today @nature.com

A solution to the pyrazole alkylation problem, leveraging S-to-NR atom replacement. Skeletal editing has strategic value, outside of late-stage!

www.nature.com/articles/s41...

Pushing the boundaries of #organosodium reagents, we are incredibly excited to report their applications in #iron #catalysed #crosscouplings with Sobi Asako and Laurean Ilies at RIKEN 🇯🇵 @naturesynthesis.bsky.social
@unibe.ch #openaccess #TeamWorkMakestheDreamWork

www.nature.com/articles/s44...

Methane Beryllation Catalyzed by a Base Metal Complex The homogeneous catalytic functionalization of methane is extremely challenging due to the relative nonpolarity and high C–H bond strength of this hydrocarbon. Here, using catalytic quantities (10 mol...

Catalytic methane functionalization and all it takes is... beryllium! We also compare the mechanisms of methane beryllation and borylation to reveal why Be finds it so easy @pubs.acs.org pubs.acs.org/doi/10.1021/...

A three-step strategy for the conversion of pyridines into benzonitriles - Nature Synthesis Bioisosteric replacement is vital in drug discovery; however, substituting core ring structures is challenging. Now, a strategy that converts pyridines into benzonitriles, via N-oxidation, photochemic...

Now online & open access:

Article by R Güdük, N Kehl, C Stavagna, MJ. Tilby, O Turner, A Ruffoni, HP. Caldora & D Leonori

A three-step strategy for the conversion of pyridines into benzonitriles

www.nature.com/articles/s44...

#ChemSky

Deciphering the mechanism of oxidative addition of aryl iodides into a red-light active bismuthinidene. Incredible team: Alexios Stamoulis, Mauro Mato, Paolo Cleto-Bruzzese, M. Leutzsch, M. Gil-Sepulcre, A. Cadranel and F. Neese.
pubs.acs.org/doi/10.1021/...

Transmetalating a challenging tetrel: introducing aryl-[Si] synthons into bismuth organometallic catalysis. Great work spearheaded by Teresa and Sophia. onlinelibrary.wiley.com/doi/10.1002/...

Excited Organic Radicals in Photoredox Catalysis Many important synthetic-oriented works have proposed excited organic radicals as photoactive species, yet mechanistic studies raised doubts about whether they can truly function as photocatalysts. This skepticism originates from the formation of (photo)redox-active degradation products and the picosecond decay of electronically excited radicals, which is considered too short for diffusion-based photoinduced electron transfer reactions. From this perspective, we analyze important synthetic transformations where organic radicals have been proposed as photocatalysts, comparing their theoretical maximum excited state potentials with the potentials required for the observed photocatalytic reactivity. We summarize mechanistic studies of structurally similar photocatalysts indicating different reaction pathways for some catalytic systems, addressing cases where the proposed radical photocatalysts exceed their theoretical maximum reactivity. Additionally, we perform a kinetic analysis to explain the photoinduced electron transfer observed in excited radicals on subpicosecond time scales. We further rationalize the potential anti-Kasha reactivity from higher excited states with femtosecond lifetimes, highlighting how future photocatalysis advancements could unlock new photochemical pathways.

Excited organic radicals in photoredox catalysis

Our perspective just published in JACS Au:

pubs.acs.org/doi/10.1021/...

Total synthesis of (−)-cylindrocyclophane A facilitated by C−H functionalization (−)-Cylindrocyclophane A is a 22-membered C2-symmetric [7.7]paracyclophane that bears bis-resorcinol functionality and six stereocenters. We report a synthetic strategy for (−)-cylindrocyclophane A th...

A true Classic in Total Synthesis by Yu, Stoltz and Davies from last year featuring the power of modern C–H activation. It has it all: carbenes, Pd catalysis, photocatalysis and an awesome target molecule. Worth a read!

www.science.org/doi/epdf/10....

Activation and C−C Coupling of Aryl Iodides via Bismuth Photocatalysis The catalytic formation of C–C bonds from aryl halides is a highly attractive but unexplored area in the emerging field of bismuth redox catalysis. We report a chemoselective bismuth-photocatalyzed a....

Final version out! Activation and C‒C Coupling of Aryl Iodides via Bismuth Photocatalysis.
Check the last report from the Cornella lab, achieving the catalytic formation of C(sp2)-C(sp2) bonds with bismuth, using not only 1 but 2 photochemical steps! #chemsky

onlinelibrary.wiley.com/doi/10.1002/...