Highly Selective C(sp³)-H Bond Oxygenation at Remote Methylenic Sites Enabled by Polarity Enhancement.

ABSTRACT: A detailed study on the C(sp³)-H bond oxygenation reactions with H₂O₂ catalyzed by the [Mn(OTf)₂(^TIPSmcp)] complex at methylenic sites of cycloalkyl and 1-alkyl substrates bearing 19 different electron-withdrawing functional groups (EW FGs) was carried out. Oxidations in MeCN were compared to the corresponding ones in the strong hydrogen bond donating (HBD) solvents 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) and nonafluoro tert-butyl alcohol (NFTBA). Formation of the products deriving from oxygenation at the most remote methylenic sites was observed, with yields, product ratios (PR) for oxygenation at the most remote over the next methylenic sites, and associated site-selectivities that significantly increased going from MeCN to H

SUBMITTER: Sisti S 

PROVIDER: S-EPMC10571082 | biostudies-literature | 2023 Oct

REPOSITORIES: biostudies-literature