A Unified Mechanism to Account for Manganese- or Ruthenium-Catalyzed Nitrile α-Olefinations by Primary or Secondary Alcohols: A DFT Mechanistic Study

Acceptorless dehydrogenative coupling (ADC) reactions generally involve a nucleophile (e.g., amine) as a coupling partner. Intriguingly, it has been reported that nitriles could also act as nucleophiles in ADC reactions, achieving the -olefination of nitriles with primary or secondary alcohols by employing a manganese or ruthenium pincer complex as the catalyst, respectively. Although different mechanisms have been postulated for the two catalytic systems, the results of our DFT mechanistic study, reported herein, have allowed us to propose a unified mechanism to account for both nitrile -olefinations. The reactions take place in four stages, namely alcohol dehydrogenation, nitrile activation to generate a nucleophilic metal species, coupling of an aldehyde or ketone with the metal species to form a C-C bond and to transfer a nitrile (C alpha-)H atom to the carbonyl group, and dehydration by transferring the protonic (N-)H to the hydroxy group. A notable feature of the coupling stage is the activation of water or alcohol to give an intermediate featuring an OH-- or OR--like group that activates a nitrile C alpha-H bond. Moreover, the mechanism can even be applied to the base (KOtBu, modeled by the (KOtBu)(4) cluster)-catalyzed Knoevenagel condensation of nitriles with ketones, which further indicates the generality of the mechanism and the resemblance of the metal pincer complexes to the (KOtBu)(4) base. We expect these in-depth mechanistic insights and the finding of the resemblance of the metal pincer complexes to the (KOtBu)(4) cluster could assist the development of new ADC reactions.