Benzylic C-H Hydroxylations in the Presence of Bioinspired Mn Complexes: the Origin of Acetate Products - Conference attendances | Sciact - CRIS-system of Boreskov Institute of Catalysis

Benzylic C-H Hydroxylations in the Presence of Bioinspired Mn Complexes: the Origin of Acetate Products Conference attendances

Language

Английский

Participant type

Стендовый

URL

http://conf.nsc.ru/mcr2019/en/mcr2019_scientific_program

Conference

XI International Conference Mechanisms of Catalytic Reactions
07-11 Oct 2019 , Сочи

Authors

Ottenbacher Roman Viktorovich ^1,2 , Sun Wei ³ , Sun Q. ³ , Bryliakov Konstantin Petrovich ^1,2

Affiliations

1	Boreskov Institute of Catalysis SB RAS
2	Novosibirsk National Research University
3	Lanzhou Institute of Chemical Physics

Herewith, the details of molecular mechanism of manganese catalyzed benzylic C-H oxidation are examined, using the formation of acetate as a mechanistic probe. The correlation between the alcohol/acetate ratio (alcohol selectivity) and the presence of electron-donating groups at the aminopyridine ligand core has been revealed. Isotopic labeling studies witness that the oxygen atom in the cumyl alcohol originates from the H2O2 molecule, while the oxygen of the acetate comes from the acetic acid. These data rule out acid-catalyzed Fischer esterification of the initially formed cumyl alcohol, and provide evidence for a different mechanism of cumyl acetate formation. Possible mechanistic alternatives are discussed.

Ottenbacher R.V. , Sun W. , Sun Q. , Bryliakov K.P.
Benzylic C-H Hydroxylations in the Presence of Bioinspired Mn Complexes: the Origin of Acetate Products
XI International Conference Mechanisms of Catalytic Reactions 07-11 Oct 2019