Tetrabutylammonium decatungstate-photosensitized alkylation of electrophilic alkenes: Convenient functionalization of aliphatic C-H bonds

Chemistry : a European Journal
Daniele DondiAngelo Albini

Abstract

Tetrabutylammonium decatungstate (TBADT, 2 x 10(-3) m) is an effective photocatalyst for the alkylation of electrophilic alkenes (0.1 m, alpha,beta-unsaturated nitriles, esters, ketones) by alkanes, alcohols, and ethers. The products are in most cases obtained in >70 % isolated yields, through an experimentally very simple procedure. The kinetics of the radical processes following initial hydrogen abstraction by excited TBADT in deoxygenated MeCN have been studied. In the absence of a trap, back hydrogen transfer from reduced tungstate is the main pathway for alkyl radicals, while alpha-hydroxyalkyl radicals are oxidized to ketones by ground-state TBADT. With both radical types the reaction ceases at a few percent conversion. However, trapping by electrophilic alkenes is followed by reduction of the radical adduct and regeneration of the catalyst, which allows the alkylation to proceed up to complete alkene conversion with the mentioned good yields of products. With a nucleophilic (alpha-hydroxyalkyl) radical, alkylation is efficient (Phi = 0.58) and can also be carried out when degassing is omitted, the only difference being a short induction period. With a less reactive (cyclohexyl) radical, the quantum yield is lower (Phi = ...Continue Reading

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Citations

Apr 14, 2016·Chemical Reviews·Davide RavelliMaurizio Fagnoni
May 15, 2015·Journal of Photochemistry and Photobiology. B, Biology·Shamsa MunirAfzal Shah
May 4, 2017·Chemistry : a European Journal·Keiichi YamadaIlhyong Ryu
Jan 21, 2015·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Davide RavelliAngelo Albini
Mar 29, 2014·Angewandte Chemie·Shira D HalperinRobert Britton
Jul 18, 2009·Chemistry : a European Journal·Daniele DondiAngelo Albini
Dec 22, 2009·Chemical Communications : Chem Comm·Stefano ProttiAngelo Albini
Aug 19, 2007·Chemical Communications : Chem Comm·Giovanni PalmisanoLeonardo Palmisano
Oct 8, 2019·Chemical Communications : Chem Comm·Pei FanChuan Wang
Oct 9, 2019·Chemistry : a European Journal·Baptiste AbadieJean-Marc Vincent
Feb 20, 2020·Chemical & Pharmaceutical Bulletin·Kenzo YahataShuji Akai
Sep 25, 2020·Organic & Biomolecular Chemistry·Stefano BoncioliniMarcus Baumann
Aug 14, 2019·Chemical Society Reviews·Zhen ChenJun-An Ma
Aug 20, 2009·Chemical Society Reviews·Manolis D TzirakisMichael Orfanopoulos
Jan 6, 2011·Chemistry : a European Journal·Davide RavelliMaurizio Fagnoni
Oct 1, 2015·Chemical Science·Guillaume DuretNicolas Blanchard
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May 18, 2018·The Journal of Organic Chemistry·Christian R Zwick, Hans Renata
May 14, 2019·Organic Letters·Vyacheslav I SupranovichAlexander D Dilman

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