Highly Enantioselective Oxidation of Spirocyclic Hydrocarbons by Bioinspired Manganese Catalysts and Hydrogen Peroxide

Bin Qiu, Daqian Xu, Qiangsheng Sun, Chengxia Miao, Yong Min Lee, Xiao Xi Li, Wonwoo Nam, Wei Sun

Research output: Contribution to journalArticlepeer-review

54 Scopus citations

Abstract

Bioinspired manganese complexes have emerged as attractive catalysts for a number of selective oxidation reactions over the past several decades. In the present study, we report the enantioselective oxidation of spirocyclic compounds with manganese complexes bearing tetradentate N4 ligands as catalysts and aqueous H2O2 as a terminal oxidant under mild conditions; spirocyclic tetralone (1a) and its derivatives bearing electron-donating and -withdrawing substituents are converted to their corresponding chiral spirocyclic β,β′-diketones with high yields and enantioselectivities. Spirocyclic indanones are also converted to the β,β′-spirobiindanones with high enantioselectivities. Indeed, the reaction expands the diversity of chiral spirocyclic diketones via a late-stage oxidative process. In addition, it is of importance to note that the catalytic reaction can be easily scaled up and the chiral spirocyclic β,β′-diketones can be transformed into diol products. In mechanistic studies, we have shown that (1) ketones were yielded as products via the initial formation of alcohols, followed by the further oxidation of the alcohols to ketones, (2) hydrogen atom (H atom) abstraction from the methylene C-H bonds of 1a by a putative Mn(V)-oxo intermediate was proposed to be the rate-determining step, and (3) the C-H bond hydroxylation of 1a by the Mn(V)-oxo species was proposed to occur via oxygen rebound mechanism. On the basis of these results, we have proposed a plausible mechanism for the selective C-H bond oxidation of hydrocarbons by bioinspired manganese catalysts and hydrogen peroxide.

Original languageEnglish
Pages (from-to)2479-2487
Number of pages9
JournalACS Catalysis
Volume8
Issue number3
DOIs
StatePublished - 2 Mar 2018

Keywords

  • asymmetric oxidation
  • C-H oxidation
  • hydrogen peroxide
  • manganese catalyst
  • manganese-oxo
  • mechanism

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