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The Functionalization of Saturated Hydrocarbons by Gif Chemistry. Part 1. Use of Superoxide and of Hydrogen Peroxide. Part 2. Use of t-Butylhydroperoxide (TBHP)

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Chemical Synthesis

Part of the book series: NATO ASI Series ((NSSE,volume 320))

Abstract

In Part 1, the Gif systems for the selective functionalization of saturated hydrocarbons based on the reactions of superoxide with FeII and of hydrogen peroxide FeIIIwith are described. [1] Both systems are relatively efficient, but not nearly so efficient as the electrochemical system developed in collaboration with Prof. G. Balavoine and Dr. Aurore Gref (Université de Paris-Sud--Orsay, France). [2] All systems afford mainly ketones. This is an unusual selectivity’ which implies a non-radical mechanism. It has been proven for the FeIII-H202 system that the activation of the FeIII is independent of the formation of ketone which comes from oxygen. The intermediate for the ketone is a hydroperoxide (derived from oxygen). [3] This intermediate controls the formation of ketone and of secondary alcohol. Addition of a number of trapping reagents such as BrCCl3 diverts the reaction from oxygenation to bromide formation. Although BrCCl3 is indeed a good trap for carbon radicals, the pattern of selectivity across a range of saturated hydrocarbons is completely different for Gif chemistry when compared with normal radical bromination. [4] The chemistry is explained in terms of an FeVoxenoid species that inserts itself into secondary carbon-hydrogen bonds (a compromise between bond strength and steric hindrance). [1] This gives an FeV intermediate A with an iron-carbon bond. This is probably rapidly reduced to the FeIII state by hydrogen peroxide. Then oxygen is inserted into the FeIII-carbon bond. Hydrolysis affords the isolateable intermediate hydroperoxide (intermediate B).

In Part 2, a system based on t.-butylHydroperoxide (TBHP) is described. This is similar to the above Gif systems, but the kinetic isotope effect is very different and the selectivity for adamantane substitution is different. However, FeIII is activated by TBHP to an FeV oxenoid which, after reaction with hydrocarbon, then reacts with oxygen to give hydroperoxide. So the pattern of intermediates A and B seen in Part 1 is maintained with TBHP. Radical chemistry may be involved in some of the reactions that involve ionic coupling to saturated hydrocarbons.

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References

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Authors and Affiliations

  1. Department of Chemistry, Texas A&M University, College Station, TX, 77843-3255, USA

    D. H. R. Barton

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  1. D. H. R. Barton
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Editors and Affiliations

  1. I.Co.C.E.A., Consiglio Nazionale delle Ricerche, Bologna, Italy

    Chryssostomos Chatgilialoglu

  2. Department of Chemistry, University of Waterloo, Waterloo, Ontario, Canada

    Victor Snieckus

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© 1996 Kluwer Academic Publishers

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Barton, D.H.R. (1996). The Functionalization of Saturated Hydrocarbons by Gif Chemistry. Part 1. Use of Superoxide and of Hydrogen Peroxide. Part 2. Use of t-Butylhydroperoxide (TBHP). In: Chatgilialoglu, C., Snieckus, V. (eds) Chemical Synthesis. NATO ASI Series, vol 320. Springer, Dordrecht. https://doi.org/10.1007/978-94-009-0255-8_26

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  • DOI: https://doi.org/10.1007/978-94-009-0255-8_26

  • Publisher Name: Springer, Dordrecht

  • Print ISBN: 978-94-010-6598-6

  • Online ISBN: 978-94-009-0255-8

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