General structure of an alkenyl peroxide

In organic chemistry, alkenyl peroxides are organic compounds bearing an alkene (R2C=CR2) residue directly at the peroxide (R−O−O−R) group, resulting in the general formula R2C=C(R)OOR. They have very weak O-O bonds and are thus generally unstable compounds.[1]

Properties

Alkenyl peroxides decompose readily by homolytic O-O bond cleavage into two radicals, generating an oxyl radical and an alkenyloxyl- or α-oxo-alkyl radical.

Decomposition of alkenyl peroxides by homolytic cleavage of the O-O bond
Decomposition of alkenyl peroxides by homolytic cleavage of the O-O bond

The significant weakness of the O-O bond can be explained by formation of the resonance stabilized alkenyloxyl radical and the strong carbonyl bond, respectively.[2] This reasoning also applies to aryl peroxides. Both compound classes thus have significantly weaker O-O bonds than other peroxides.[2][3] Because of this weak bond, alkenyl peroxides are generally only postulated as reactive intermediates. An exception is the case of some few heteroarylperoxides, which were long-lived enough to be characterized.[4]

Occurrence

In the atmosphere

Alkenyl hydroperoxides (R1 = H) have been postulated as reactive intermediates in atmospheric chemistry.[5][6] They are formed via ozonolysis of alkenes in the atmosphere and form hydroxyl radicals upon decay, which play an important role in the decomposition of pollutants in the air. During day-time, hydroxyl radicals form predominantly photochemically by irradiation with light; whereas in the dark during night-time, the formation via alkenyl peroxides is believed to be their major source.[5]

In solution

Alkenyl peroxides can be formed by acid catalyzed condensation of ketones with organic hydroperoxides or hydrogen peroxide. This has been suggested based on the characterization of the corresponding products of decomposition.[3] Alkenyl peroxides could also occur as unwanted byproducts in the Baeyer–Villiger oxidation when using hydrogen peroxide, which would diminish the effectiveness of this reaction.[3]

Applications

The radicals formed from alkenyl peroxides can be utilized in organic radical reactions. For example, they can mediate hydrogen atom abstraction reactions and thus lead to the functionalization of C-H bonds,[7] or they can be used to introduce ketone residues by addition of the alkenyloxyl radicals to alkenes.[8][9][10]

References

  1. ↑ Klussmann, Martin (2018). "Alkenyl and Aryl Peroxides". Chemistry – A European Journal. 24 (18): 4480–4496. doi:10.1002/chem.201703775. PMID 29205531.
  2. 1 2 Sebbar, Nadia; Bozzelli, Joseph W.; Bockhorn, Henning (2004). "Thermochemical Properties, Rotation Barriers, Bond Energies, and Group Additivity for Vinyl, Phenyl, Ethynyl, and Allyl Peroxides". The Journal of Physical Chemistry A. 108 (40): 8353–8366. Bibcode:2004JPCA..108.8353S. doi:10.1021/jp031067m.
  3. 1 2 3 Schweitzer‐Chaput, Bertrand; Kurtén, Theo; Klussmann, Martin (2015). "Acid‐Mediated Formation of Radicals or Baeyer–Villiger Oxidation from Criegee Adducts". Angewandte Chemie International Edition. 54 (40): 11848–11851. doi:10.1002/anie.201505648. PMID 26267787.
  4. ↑ H. Kropf, M. Ball, Liebigs Ann. Chem. 1976, 2331–2338.
  5. 1 2 Vereecken, Luc; Francisco, Joseph S. (2012). "Theoretical studies of atmospheric reaction mechanisms in the troposphere". Chemical Society Reviews. 41 (19): 6259–6293. doi:10.1039/C2CS35070J. PMID 22660412..
  6. ↑ Gutbrod, Roland; Schindler, Ralph N.; Kraka, Elfi; Cremer, Dieter (1996). "Formation of OH radicals in the gas phase ozonolysis of alkenes: The unexpected role of carbonyl oxides". Chemical Physics Letters. 252 (3–4): 221–229. Bibcode:1996CPL...252..221G. doi:10.1016/0009-2614(96)00126-1..
  7. ↑ M. Klussmann, B. Schweitzer-Chaput, Synlett 2016, 27, 190-202.doi:10.1055/s-0035-1560706
  8. ↑ Schweitzer‐Chaput, Bertrand; Demaerel, Joachim; Engler, Hauke; Klussmann, Martin (2014). "Acid‐Catalyzed Oxidative Radical Addition of Ketones to Olefins". Angewandte Chemie International Edition. 53 (33): 8737–8740. doi:10.1002/anie.201401062. PMID 24777703..
  9. ↑ Klussmann, Martin; Boess, Esther; Karanestora, Sofia; Bosnidou, Alexandra-Eleni; Schweitzer-Chaput, Bertrand; Hasenbeck, Max (2015). "Synthesis of Oxindoles by Brønsted Acid Catalyzed Radical Cascade Addition of Ketones". Synlett. 26 (14): 1973–1976. doi:10.1055/s-0034-1381052. S2CID 97480352.
  10. ↑ Xia, Xiao-Feng; Zhu, Su-Li; Zeng, Minglu; Gu, Zhen; Wang, Haijun; Li, Wei (2015). "Acid-catalyzed cascade radical addition/Cyclization of arylacrylamides with ketones". Tetrahedron. 71 (36): 6099–6103. doi:10.1016/j.tet.2015.06.106..
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