Titanium Tetrachloride-Magnesium

In Situ Catalyst Generation and Benchtop-Compatible Entry Points for TiII/TiIV Redox Catalytic Reactions

“…For example, Cp 2 TiX-based reagents/intermediates are well-established in a diverse array of single-electron reactions (e.g., epoxide ring opening, ring-forming reactions, and HAT reactions), which commonly use either Mn or Zn alongside a weak acid. , The ability to access the two-electron manifold is likely an effect of having weakly donating halide ligands on Ti in combination with strongly π-accepting substrates . Interestingly, many common metal reductants used in Ti-mediated reactions (e.g., Al, Mn, Mg) fail for the [2 + 2 + 1] pyrrole synthesis; this may be due to over-reduction of the Ti intermediates, metal salt complex formation (e.g., [Mg­(THF) 6 ]­[TiCl 5 THF] or (TiCl 3 ) 3 AlCl 3 ), or kinetically slow reductions under these conditions …”