Simple salts of abundant metals (Fe, Bi, and Ti) supported on montmorillonite as efficient and recyclable catalysts for regioselective intramolecular and intermolecular hydroalkoxylation reactions of double bonds and tandem processes

The transfer of catalytic hydroalkoxylation reactions of olefins from homogeneous to heterogeneous conditions has been studied using two types of solid catalysts, namely montmorillonite (MMT) doped with metal cations and metal nanoparticles supported on oxides. In the case of intramolecular reactions, 38-99% yields of cyclic ethers have been obtained using Fe-MMT and Bi-MMT both in CH 3 NO 2 and dimethyl carbonate (DMC) compared with other supported metal salts or metal nanoparticles. In the case of more challenging intermolecular reactions, conversions up to 72% and yields up to 54% were obtained with metal-doped MMT as well, such as Fe-, Bi-, and Ti-MMT. In this paper, we detail the substrate scope and limitations for both classes of reactions and tandem processes, their transposition in flow and some mechanistic insights concerning the active species, in processes identified as truly heterogeneously catalysed. As a general trend, it was observed that trisubstituted double bonds allowed the best results both in intra- and intermolecular reactions. The transfer of homogeneous catalysts onto heterogeneous ones in the case of Fe-MMT and Bi-MMT was successful and even allowed enhanced catalytic activities in the case of Bi-MMT. Montmorillonites doped with metal cations are efficient and recyclable catalysts for hydroalkoxylation reactions and amenable to flow chemistry.