NEMESIS project: Pioneering sustainable and cost-effective nickel-catalyzed synthesis of allylic amines

In a move toward sustainable chemistry, Prof. Arjan Kleij, group leader at the Institute of Chemical Research of Catalonia (ICIQ-CERCA) has launched the NEMESIS project, aiming to revolutionize the synthesis of highly substituted allylic amines using nickel-based catalysts. This innovative project, officially titled “Nickel-Catalyzed Regio- and Enantioselective Synthesis of Highly Substituted Allylic Amines”, promises to address challenges in the field of organic chemistry while promoting environmental sustainability and cost-effectiveness.

The NEMESIS project, funded under Spain’s “Proyectos de Colaboración Internacional 2021” program, underscores the country’s commitment to supporting high-level scientific and technical collaborations on a global scale. By enhancing Spain’s presence in international R&D and fostering excellence within its Science, Technology, and Innovation System, this initiative aligns with the strategic priorities of the European Research Area and beyond.

About NEMESIS

Traditionally, transition metal-catalyzed asymmetric allylic alkylation (AAA) has been a powerful tool in constructing various carbon-carbon and carbon-heteroatom bonds. However, current methodologies, primarily relying on expensive and scarce late transition metals like rhodium, iridium, and palladium, have seen limited success in synthesizing densely substituted linear allylic amines with precise stereocontrol. The NEMESIS project seeks to overcome these limitations by developing new protocols utilizing more abundant and economically viable nickel catalysts.

Nickel, a first-row transition metal, stands out for its unique ability to form diverse sigma- and pi-Ni(allyl) complexes, making it an attractive candidate for AAA reactions. The NEMESIS project aims to create a positive synergy between established allylic chemistry and nickel catalysis, paving the way for sustainable and stereodefined synthetic routes for complex multi-substituted allylic amines. Specifically, the project will target the synthesis of linear allylic amines with stereodefined tri- and tetrasubstituted double bonds, as well as the challenging asymmetric preparation of di-alpha substituted branched allylic amines.

Prof. Kleij’s vision for NEMESIS extends beyond mere scientific discovery. The project is poised to set new standards in sustainability and cost-effectiveness within the allylic alkylation reactions. By focusing on the utilization of nickel, NEMESIS aims to develop economically attractive protocols that can prepare both known and novel chiral allylic amine intermediates crucial for pharmaceutical and fine chemical development. The project’s hypothesis hinges on fine-tuning the supporting ligands, metal precursors, and reaction conditions to offer a sustainable and cost-efficient solution in this domain.

The successful development of nickel-based AAA catalysis not only promises to advance organic chemistry but also holds significant potential for technology transfer and implementation in global academic and industrial laboratories. With the backing of ICIQ’s specialized Knowledge and Technology Transfer Unit, the NEMESIS project is well-positioned to protect and commercialize its groundbreaking outcomes, potentially leading to valuable intellectual property and patent applications.

Proyecto PCI2021-122021-2B financiado por MCIN/AEI/10.13039/501100011033 y por la Unión Europea “NextGenerationEU/PRTR”