Mechanisms of hydrogen-, oxygen-, and electron-transfer reactions of cumylperoxyl radical

Journal of the American Chemical Society
Shunichi FukuzumiYoshihito Watanabe

Abstract

Rates of hydrogen-transfer reactions from a series of para-substituted N,N-dimethylanilines to cumylperoxyl radical and oxygen-transfer reactions from cumylperoxyl radical to a series of sulfides and phosphines have been determined in propionitrile (EtCN) and pentane at low temperatures by use of ESR. The observed rate constants exhibit first-order and second-order dependence with respect to concentrations of N,N-dimethylanilines. This indicates that the hydrogen- and oxygen-transfer reactions proceed via 1:1 charge-transfer (CT) complexes formed between the substrates and cumylperoxyl radical. The primary kinetic isotope effects are determined by comparing the rates of N,N-dimethylanilines and the corresponding N,N-bis(trideuteriomethyl)anilines. The isotope effect profiles are quite different from those reported for the P-450 model oxidation of the same series of substrates. Rates of electron-transfer reactions from ferrocene derivatives to cumylperoxyl radical have also been determined by use of ESR. The catalytic effects of Sc(OTf)(3) (OTf = triflate) on the electron-transfer reactions are compared with those of Sc(OTf)(3) on the hydrogen- and oxygen-transfer reactions. Such comparison provides strong evidence that the hydr...Continue Reading

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Citations

Aug 9, 2012·Accounts of Chemical Research·Mildred QuintanaMaurizio Prato
Aug 30, 2017·Chemistry : a European Journal·Julia StanekSonja Herres-Pawlis
Jun 23, 2018·Angewandte Chemie·Congjun Yu, Frederic W Patureau
Sep 26, 2015·Chemistry : a European Journal·Shunichi FukuzumiWonwoo Nam
Jul 21, 2006·Organic & Biomolecular Chemistry·Shinro YasuiTetsuro Majima
Sep 29, 2009·Angewandte Chemie·Luca ValgimigliDerek A Pratt
Nov 7, 2012·Chemistry : a European Journal·Shunichi FukuzumiTetsuya Ojiri
Nov 6, 2012·Chemical Communications : Chem Comm·Riccardo AmoratiMario C Foti
Dec 24, 2013·Dalton Transactions : an International Journal of Inorganic Chemistry·Subrata KunduKallol Ray
Jun 18, 2009·Journal of the American Chemical Society·Takahiro MatsumotoMasatatsu Suzuki
Jun 3, 2010·Langmuir : the ACS Journal of Surfaces and Colloids·Jun Rye ChoiTetsuro Majima
Nov 27, 2009·The Journal of Physical Chemistry. B·Tomonori KawashimaShunichi Fukuzumi
Apr 28, 2007·Accounts of Chemical Research·Shinobu Itoh, Shunichi Fukuzumi
Jun 24, 2014·Journal of the American Chemical Society·Jung Yoon LeeKenneth D Karlin
Jan 23, 2019·The Journal of Organic Chemistry·Massimo BiettiMichela Salamone
May 9, 2012·Journal of the American Chemical Society·Mildred QuintanaMaurizio Prato
Sep 4, 2014·The Journal of Organic Chemistry·Pu LuoJoseph P Dinnocenzo
May 26, 2018·The Journal of Organic Chemistry·Sergio M BonesiAngelo Albini
Aug 5, 2017·The Journal of Organic Chemistry·Sergio M BonesiAngelo Albini

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