BiREDOX · Bi(III)/Bi(V) Redox Catalysis for Organic Synthesis

The continued use of non-earth abundant and toxic metals as catalysts represents a major challenge in catalysis that must be addressed if true sustainable processes are to be developed. In this regard, the development of new low-cost and non-toxic catalysts would be highly desirable with significant impact to the environment and ultimately, our society. To this end, bismuth represents an attractive alternative for the development of catalytic alternatives that secure sustainable and environmentally friendly approaches for organic synthesis. Despite the wide range of bismuth salts capable of performing organic transformations, their ability to participate in catalytic redox processes is largely unknown. Hence, the major reason for this underdevelopment is the requirement of strong oxidants to achieve a higher oxidation state at the metal center, rendering a catalytic cycle unfeasible. Thus, this project aims at the rational design of novel bismuth complexes to be engaged in catalytic Bi(III)/Bi(V) redox processes, which will represent an unprecedented strategy for organic synthesis. The research proposal presented herein relies on the design of strained Bi complexes to unlock the use of N-fluoro/trifluoromethyl salts and of aryliodonium and diazonium species, to serve as mild oxidants for Bi(III) centers. In addition, reductive elimination from Bi(V) will also be studied in detail to fully elucidate the basic steps of a Bi(III)/Bi(V) redox cycle. Additionally, the ultimate goal of this proposal is the implementation of such bismuth complexes as catalysts in organic synthesis, thus opening up new possibilities to explore a new chemical space. Thus, this project aims to provide a greener alternative to the scarce and expensive second- and third-row transition metals typically used in catalysis, particularly focusing on both their replacement for bismuth salts and the discovery of novel reactions and selectivities previously unknown.