Abstract
AbstractWe describe a unique catalytic system with an efficient coupling of Ti‐ and Cr‐catalysis in a reaction network that allows the use of [BH4]− as stoichiometric hydrogen atom and electron donor in catalytic radical chemistry. The key feature is a relay hydrogen atom transfer from [BH4]− to Cr generating the active catalysts under mild conditions. This enables epoxide reductions, regiodivergent epoxide opening and radical cyclizations that are not possible with cooperative catalysis with radicals or by epoxide reductions via Meinwald rearrangement and ensuing carbonyl reduction. No typical SN2‐type reactivity of [BH4]− salts is observed.
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