Revisiting the Synthesis and Nucleophilic Reactivity of an Anionic Copper Superoxide Complex.

ABSTRACT: The addition of 1 equiv of KO₂ and Kryptofix222 (Krypt) in CH₃CN to a solution of LCu(CH₃CN) [L = N, N'-bis(2,6-diisopropylphenyl)-2,6-pyridinecarboxamide] in tetrahydrofuran at -80 °C yielded [K(Krypt)][LCuO₂], the enhanced stability of which enabled reexamination of its reactivity with 2-phenylpropionaldehyde (2-PPA). Mechanistic and product analysis studies revealed that [K(Krypt)][LCuO₂] reacts with wet 2-PPA to form [LCuOH]^-, which then deprotonates 2-PPA to yield the copper(II) enolate complex [LCu(OC═C(Me)Ph)]^-. Acetophenone was observed upon workup of this complex or mixtures of KO₂ and 2-PPA alone, in support of an alternative mechanism(s) to the one proposed previously involving an initial nuc

SUBMITTER: Bailey WD 

PROVIDER: S-EPMC6548509 | biostudies-literature | 2019 Apr

REPOSITORIES: biostudies-literature