Chemoselective Aliphatic C-H Bond Oxidation Enabled by Polarity Reversal

ACS Central Science
Valeria DantignanaMiquel Costas

Abstract

Methods for selective oxidation of aliphatic C-H bonds are called on to revolutionize organic synthesis by providing novel and more efficient paths. Realization of this goal requires the discovery of mechanisms that can alter in a predictable manner the innate reactivity of these bonds. Ideally, these mechanisms need to make oxidation of aliphatic C-H bonds, which are recognized as relatively inert, compatible with the presence of electron rich functional groups that are highly susceptible to oxidation. Furthermore, predictable modification of the relative reactivity of different C-H bonds within a molecule would enable rapid diversification of the resulting oxidation products. Herein we show that by engaging in hydrogen bonding, fluorinated alcohols exert a polarity reversal on electron rich functional groups, directing iron and manganese catalyzed oxidation toward a priori stronger and unactivated C-H bonds. As a result, selective hydroxylation of methylenic sites in hydrocarbons and remote aliphatic C-H oxidation of otherwise sensitive alcohol, ether, amide, and amine substrates is achieved employing aqueous hydrogen peroxide as oxidant. Oxidations occur in a predictable manner, with outstanding levels of product chemoselect...Continue Reading

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Citations

Jul 25, 2018·Chemical Communications : Chem Comm·Michela MilanMiquel Costas
Jul 28, 2018·Angewandte Chemie·Hans SterckxBert U W Maes
Jun 7, 2019·Chemistry : a European Journal·Michiel Janssen, Dirk E De Vos
Jan 4, 2020·Angewandte Chemie
Feb 17, 2018·Angewandte Chemie·Gabriele LaudadioTimothy Noël
Jun 1, 2019·Nature Reviews. Chemistry·Huw M L Davies, Kuangbiao Liao
Oct 20, 2018·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·A Sofia SantosM Manuel B Marques
Feb 13, 2021·The Journal of Organic Chemistry·Olga V KushchAlexander N Shendrik
Jan 19, 2021·Angewandte Chemie·Alastair J McMillanDaniele Leonori
Apr 6, 2021·ACS Catalysis·Silvia D'AgostiniDennis G H Hetterscheid
Jun 25, 2021·Chemical Science·Trisha BhattacharyaDebabrata Maiti
Jul 22, 2021·The Journal of Physical Chemistry Letters·Xiaomeng FanJie Xu
Aug 7, 2021·Chemical Reviews·Luca CapaldoMaurizio Fagnoni
Aug 11, 2021·Chemical Communications : Chem Comm·Masatoshi ShibuyaYoshihiko Yamamoto
Aug 7, 2018·Accounts of Chemical Research·Michela MilanMassimo Bietti
May 24, 2019·The Journal of Organic Chemistry·Francesca BartocciniGiovanni Piersanti
May 19, 2020·Organic Letters·Sophia G RobinsonMatthew S Sigman
Jan 3, 2019·Journal of the American Chemical Society·James B C MackJ Du Bois
Mar 17, 2018·Organic Letters·Robert M B DyerMichael K Hilinski
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Oct 6, 2021·Chemical Record : an Official Publication of the Chemical Society of Japan ... [et Al.]·Miquel Costas
Dec 3, 2021·Journal of the American Chemical Society·McKenna K GoetzJohn S Anderson

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