C-Alkylation of Various Carbonucleophiles with Secondary Alcohols under Co III -Catalysis

Priyanka Chakraborty (1) , Nidhi Garg (1) , Eric Manoury (2) , Rinaldo Poli (2) , Basker Sundararaju (1)

1 IIT Kanpur - Department of Chemistry [Kanpur]
2 LCC - Laboratoire de chimie de coordination

Oxindoles have been successfully α-alkylated under Cp*CoIII catalysis by a vast array of secondary alcohols, including cyclic, acyclic, symmetrical, and unsymmetrical, to produce C-alkylated oxindoles. This protocol was also extended to the α-alkylation of N,N-dimethyl barbituric acid and benzyl cyanides. The kinetic profile and other preliminary mechanistic investigations suggest a first-order reaction rate in oxindoles and catalysts. A plausible catalytic cycle is proposed on the basis of the kinetic profile, of other preliminary mechanistic investigations, and of previous mechanistic studies on similar transformations, whereas density functional theory calculations provide insight into the nature of the active species.

Mots clés: C-alkylation; Secondary alcohol; Dehydrogenation; Cobalt; Borrowing hydrogen catalysis

Domaines: Catalyse; Chimie organique

Priyanka Chakraborty, Nidhi Garg, Eric Manoury, Rinaldo Poli, Basker Sundararaju. C-Alkylation of Various Carbonucleophiles with Secondary Alcohols under Co III -Catalysis. ACS Catalysis, 2020, 10 (14), pp.8023-8031. ⟨10.1021/acscatal.0c01728⟩. ⟨hal-02947876⟩