Catalysis by [Ga₄ L₆ ]^12- Metallocage on the Nazarov Cyclization: The Basicity of Complexed Alcohol is Key.

ABSTRACT: The Nazarov cyclization is investigated in solution and within K₁₂ [Ga₄ L₆ ] supramolecular organometallic cage by means of computational methods. The reaction needs acidic condition in solution but works at neutral pH in the presence of the metallocage. The reaction steps for the process are analogous in both media: (a) protonation of the alcohol group, (b) water loss and (c) cyclization. The relative Gibbs energies of all the steps are affected by changing the environment from solvent to the metallocage. The first step in the mechanism, the alcohol protonation, turns out to be the most critical one for the acceleration of the reaction inside the metallocage. In order to calculate the relative stability of protonated alcohol inside the cavity, we propose a

SUBMITTER: Norjmaa G 

PROVIDER: S-EPMC9804567 | biostudies-literature | 2022 Oct

REPOSITORIES: biostudies-literature