Decades of improvement in the cross-coupling arena have provided a highly modular toolkit for bond construction in organic synthesis. In addition, the introduction of an alkene as a third component has recently emerged as a viable catalytic strategy for quickly enhancing molecular complexity. Indeed, in these transformations, two carbogenic partners are distributed across the C=C bond, resulting in 1,2-dicarbofunctionalization offering strategic advantages in synthesis. However, existing metal-catalyzed methodologies (Pd, Ni and Cu) to perform such reactions suffer from three main limitations: (i) use of biased alkenes or directing groups to enable selective 1.2 difunctionalization; (ii) competitive side beta-hydride elimination; and (iii) nature of coupling partners (organometallic or activated). Consequently, there is a unique opportunity to develop unprecedented 1,2-dicarbofunctionalization reactions of non-biased alkenes that will use readily available starting materials and a metal that won’t undergo rapid beta-hydride elimination. Manganese, a first-row transition metal, is abundant, inexpensive, and non-toxic. It participates in myriad of transformations including radical and C-C bond formation processes. More importantly, manganese-based intermediates do not easily undergo beta-hydride elimination. Therefore, this project aims to develop unprecedented manganese-catalyzed 1,2-dicarbofunctionalization reactions of non-biased alkenes. The use of readily available compounds and the absence of a directing group will expand the scope of such transformations which will undoubtedly serve as a powerful strategy for building complex molecular scaffolds.
Monsieur Julien VANTOUROUT (Institut de chimie et biochimie moléculaires et supramoléculaires)
The author of this summary is the project coordinator, who is responsible for the content of this summary. The ANR declines any responsibility as for its contents.
ICBMS Institut de chimie et biochimie moléculaires et supramoléculaires
Help of the ANR 208,144 euros
Beginning and duration of the scientific project: March 2023 - 42 Months