Jump to main content
Jump to site search

Issue 42, 2020
Previous Article Next Article

The formyloxyl radical: electrophilicity, C–H bond activation and anti-Markovnikov selectivity in the oxidation of aliphatic alkenes

Author affiliations

Abstract

In the past the formyloxyl radical, HC(O)O˙, had only been rarely experimentally observed, and those studies were theoretical-spectroscopic in the context of electronic structure. The absence of a convenient method for the preparation of the formyloxyl radical has precluded investigations into its reactivity towards organic substrates. Very recently, we discovered that HC(O)O˙ is formed in the anodic electrochemical oxidation of formic acid/lithium formate. Using a [CoIIIW12O40]5− polyanion catalyst, this led to the formation of phenyl formate from benzene. Here, we present our studies into the reactivity of electrochemically in situ generated HC(O)O˙ with organic substrates. Reactions with benzene and a selection of substituted derivatives showed that HC(O)O˙ is mildly electrophilic according to both experimentally and computationally derived Hammett linear free energy relationships. The reactions of HC(O)O˙ with terminal alkenes significantly favor anti-Markovnikov oxidations yielding the corresponding aldehyde as the major product as well as further oxidation products. Analysis of plausible reaction pathways using 1-hexene as a representative substrate favored the likelihood of hydrogen abstraction from the allylic C–H bond forming a hexallyl radical followed by strongly preferred further attack of a second HC(O)O˙ radical at the C1 position. Further oxidation products are surmised to be mostly a result of two consecutive addition reactions of HC(O)O˙ to the C[double bond, length as m-dash]C double bond. An outer-sphere electron transfer between the formyloxyl radical donor and the [CoIIIW12O40]5− polyanion acceptor forming a donor–acceptor [D+–A] complex is proposed to induce the observed anti-Markovnikov selectivity. Finally, the overall reactivity of HC(O)O˙ towards hydrogen abstraction was evaluated using additional substrates. Alkanes were only slightly reactive, while the reactions of alkylarenes showed that aromatic substitution on the ring competes with C–H bond activation at the benzylic position. C–H bonds with bond dissociation energies (BDE) ≤ 85 kcal mol−1 are easily attacked by HC(O)O˙ and reactivity appears to be significant for C–H bonds with a BDE of up to 90 kcal mol−1. In summary, this research identifies the reactivity of HC(O)O˙ towards radical electrophilic substitution of arenes, anti-Markovnikov type oxidation of terminal alkenes, and indirectly defines the activity of HC(O)O˙ towards C–H bond activation.

Graphical abstract: The formyloxyl radical: electrophilicity, C–H bond activation and anti-Markovnikov selectivity in the oxidation of aliphatic alkenes

Back to tab navigation

Supplementary files

Article information


Submitted
07 Sep 2020
Accepted
02 Oct 2020
First published
02 Oct 2020

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2020,11, 11584-11591
Article type
Edge Article

The formyloxyl radical: electrophilicity, C–H bond activation and anti-Markovnikov selectivity in the oxidation of aliphatic alkenes

M. Somekh, M. A. Iron, A. M. Khenkin and R. Neumann, Chem. Sci., 2020, 11, 11584
DOI: 10.1039/D0SC04936K

This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence. Material from this article can be used in other publications provided that the correct acknowledgement is given with the reproduced material and it is not used for commercial purposes.

Reproduced material should be attributed as follows:

  • For reproduction of material from NJC:
    [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the Centre National de la Recherche Scientifique (CNRS) and the RSC.
  • For reproduction of material from PCCP:
    [Original citation] - Published by the PCCP Owner Societies.
  • For reproduction of material from PPS:
    [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the European Society for Photobiology, the European Photochemistry Association, and RSC.
  • For reproduction of material from all other RSC journals:
    [Original citation] - Published by The Royal Society of Chemistry.

Information about reproducing material from RSC articles with different licences is available on our Permission Requests page.


Social activity

Search articles by author

Spotlight

Advertisements