Manganese-catalyzed Intermolecular Alkene Carbofunctionalization – MANIAC

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.