Periodic Reporting for period 4 - MetalloRadiCat (Metalloradical Catalysis - From Fundamental Studies to Applications)
Periodo di rendicontazione: 2024-11-01 al 2025-10-31
The MetalloRadiCat project combines experimental and computational approaches to fundamentally investigate and address some of the most challenging aspects of homogeneous metalloradical catalysis.
From the outset, the project focused on mechanistically exploring and establishing metalloradical catalysis as a distinct and controllable reactivity paradigm through an integrated program combining organometallic synthesis, mechanistic studies, computation, and method development. A central result was the demonstration that metalloradicals exhibit reactivity principles fundamentally different from classical organic radicals. Ni(I) metalloradical catalysis was shown to enable reversible and stereochemically well-defined transformations under mild conditions, validating metalloradical catalysis as a predictable platform for frontier reactivity. In parallel, predictive strategies for controlling metal oxidation state and speciation were developed by integrating machine-learning-guided ligand design. Building on this understanding, the project delivered new catalytic concepts for selective synthesis. For example, Ni-catalyzed chain walking enabled remote functionalization with catalyst-controlled positional and geometric selectivity, while robust and air-stable Pd(I) dimer catalysts allowed selective olefin migration and C–C bond formation under ambient conditions. These studies established odd-oxidation-state catalysts as practical tools for selective transformations.
Beyond the original scope, orthogonal and modular synthesis platforms were developed using organogermanes as selectively activatable functional handles, enabling chemoselective bond formation and sequential diversification of Csp³ centers. In the final phase, the project also expanded accessible chemical space through the development of general and mild routes to previously unavailable fluorinated carbonyl compounds relevant to medicinal, agrochemical, and materials research.
Overall, the project achieved all its objectives, delivering both conceptual advances and broadly applicable catalytic technologies. Results were disseminated through publications in leading international journals and presentations at major international conferences and are being exploited through their adoption as general design principles and synthetic tools by the wider research community.
Beyond the original scope, orthogonal and modular synthesis platforms were developed using organogermanes as selectively activatable functional handles, enabling chemoselective bond formation and sequential diversification of Csp³ centers. In the final phase, the project also expanded accessible chemical space through the development of general and mild routes to previously unavailable fluorinated carbonyl compounds relevant to medicinal, agrochemical, and materials research.
Overall, the project achieved all its objectives, delivering both conceptual advances and broadly applicable catalytic technologies. Results were disseminated through publications in leading international journals and presentations at major international conferences and are being exploited through their adoption as general design principles and synthetic tools by the wider research community.
The project advanced the state of the art by establishing metalloradical catalysis as a controllable and predictable platform. It revealed new reactivity principles that enable mild, selective and previously inaccessible chemical transformations. In addition, the project expanded accessible chemical space and provided new tools for sustainable synthesis or to accelerate synthetic access. All objectives were achieved, laying the foundation for future developments in catalysis and molecular design.