Orbital‐Driven Insights into Enantioselective Hydrofunctionalization of Alkenes Catalyzed by Co‐Salen Complexes: Study on Singlet and Triplet States

The Co(salen) ([LCo(II)]) mediated hydrofunctionalization of alkenes is a highly significant method for forming enantioselective products. In this work, we conducted comprehensive computational investigations to gain insights of the reaction mechanism. The orbital analysis and intrinsic bond orbital analysis (IBO) were utilized to unravel the flow of electrons during the progress of the reaction. We explored various spin state surfaces to understand the possible pathways for the reaction. Initially, [LCo(II)] reacts with an oxidant tertbutyl peroxybenzoate, yielding [LCo(III)OC(O)Ph] and [LCo(III)O^tBu]. Subsequently, [LCo(III)OC(O)Ph] reacts with silane to form cobalt hydride ([LCo(III)H]), with the triplet spin state surface being the preferred pathway, featuring an energy barrier of 14.2 kcal mol^-1. IBO analysis across this step revealed that it involves the transfer of hydrogen as a hydride. Subsequently, the [LCo(III)H] complex in a triplet spin state undergoes a minimum energy crossing point (MECP) to transition into the singlet spin state, representing its most stable configuration. The [LCo(III)H] complex further reacts with styrene via hydrogen atom transfer on the singlet spin state surface, followed by oxidation and subsequent reaction with indole on the doublet spin surface to yield the hydrofunctionalized product. This work also explores potential enantioselective steps in the reaction.