A general bismuth-based platform for the catalytic construction of carbon–nitrogen bonds and beyond.

Project Information

ClaN-Bi

Grant agreement ID: 101105383

DOI

10.3030/101105383

Project closed

EC signature date 21 March 2023

Start date 1 May 2023

End date 30 April 2025

Funded under

• Marie Skłodowska-Curie Actions (MSCA)

Total cost

No data

EU contribution

€ 173 847,36

Coordinated by

MAX PLANCK INSTITUT FUER KOHLENFORSCHUNG
Germany

Periodic Reporting for period 1 - ClaN-Bi (A general bismuth-based platform for the catalytic construction of carbon–nitrogen bonds and beyond.)

Reporting period: 2023-05-01 to 2025-04-30

Summary of the context and overall objectives of the project

The creation of carbon-nitrogen (C-N) and carbon-carbon (C-C) bonds is a cornerstone of modern chemistry, enabling the synthesis of complex molecules used in medicines, agriculture, and materials. Top-selling drugs rely on C-N bonds to achieve their function, yet traditional methods to form these bonds use expensive and toxic metals like palladium, posing environmental and cost challenges. The ClaN-Bi project aimed to transform this landscape by harnessing bismuth, a non-toxic, as a sustainable catalyst for these critical reactions. Recent discoveries have shown that bismuth can mimic transition metals by cycling through different chemical states (Bi(I) to Bi(III) or Bi(III) to Bi(V)) and generate reactive radicals, offering new pathways for chemical synthesis. Within this project, we pursued two key objectives: 1) Develop new bismuth-based chemical processes, focusing on radical-generating steps and transition metal-like reactions to form C-N and C-C bonds; 2) Establish catalytic cycles using low-valent bismuth to create these bonds efficiently, providing a greener and cheaper alternative to conventional methods. By integrating radical and polar mechanisms, often aided by light-driven (photochemical) steps, the project sought to unlock bismuth’s untapped potential in catalysis.

Over the course of this action, we have demonstrated bismuth’s potential to catalyze innovative reactions, inspiring new research directions in chemistry. These advancements could lower production costs for medicines and agrochemicals, making them more accessible.

Work performed from the beginning of the project to the end of the period covered by the report and main results achieved so far

Within this project, we synthesized and studied new bismuth compounds to develop catalytic processes for forming C-N and C-C bonds. Using advanced analytical techniques, we explored how bismuth complexes generate carbon-centered radicals and cycle through redox states (Bi(I) to Bi(III)). A novel radical generation strategy enabled two major achievements in C-C bond formation: first, a bismuth-catalyzed method to add trifluoromethyl groups to molecules, a critical step in drug discovery; second, a bismuth-catalyzed process to form cyclopropane rings, essential building blocks for pharmaceuticals and agrochemicals. The knowledge gathered during the action is instrumental in promoting C-N and C-Het bond formation.

Progress beyond the state of the art and expected potential impact (including the socio-economic impact and the wider societal implications of the project so far)

The findings of this action open new avenues for main group elements in catalysis, challenging the reliance on traditional metals. To ensure further uptake, additional research is needed to optimize C-N bond formation and explore industrial applications. Support for commercialization, such as partnerships with pharmaceutical companies, intellectual property protection, and regulatory frameworks for bismuth-based catalysts, will be crucial. The project’s results, shared openly, lay a foundation for future innovations in green chemistry, with potential to impact global chemical production.

Bi-redox photocatalysis for organic synthesis