Metal-Free and Redox-Neutral Conversion of Organotrifluoroborates into Radicals Enabled by Visible Light

Angewandte Chemie
Wenbo LiuChao-Jun Li

Abstract

Converting organoboron compounds into the corresponding radicals has broad synthetic applications in organic chemistry. To achieve these transformations, various strong oxidants such as Mn(OAc)3 , AgNO3 /K2 S2 O8 , and Cu(OAc)2 , in stoichiometric amounts are required, proceeding by a single-electron transfer mechanism. Established herein is a distinct strategy for generating both aryl and alkyl radicals from organotrifluoroborates through an SH 2 process. This strategy is enabled by using water as the solvent, visible light as the energy input, and diacetyl as the promoter in the absence of any metal catalyst or redox reagent, thereby eliminating metal waste. To demonstrate its synthetic utility, an efficient acetylation to prepare valuable aryl (alkyl) methyl ketones is described and applications to construct C-C, C-I, C-Br, and C-S bonds are also feasible. Experimental evidence suggests that triplet diacetyl serves as the key intermediate in this process.

References

Feb 14, 2002·Chemical Reviews·C Ollivier, P Renaud
Jan 18, 2003·The Journal of Organic Chemistry·Ayhan S DemirMustafa Emrullahoglu
Aug 14, 2003·Chemical Reviews·Tamio Hayashi, Kaori Yamasaki
Jul 27, 2006·Journal of the American Chemical Society·Gary A Molander, Daniel E Petrillo
Jan 30, 2007·Accounts of Chemical Research·Gary A Molander, Noel Ellis
Apr 6, 2007·The Journal of Organic Chemistry·Gary A Molander, David J Cooper
Dec 22, 2007·Chemical Reviews·Sylvain Darses, Jean-Pierre Genet
Aug 4, 2010·Chemical Reviews·Nuno R CandeiasPedro M P Gois
Aug 20, 2010·Organic Letters·Arne Dickschat, Armido Studer
Sep 4, 2010·Journal of the American Chemical Society·Ian B SeiplePhil S Baran
Oct 12, 2010·Angewandte Chemie·Geoffroy SorinLouis Fensterbank
Jan 5, 2011·The Journal of Organic Chemistry·Gary A Molander, Livia N Cavalcanti
Mar 12, 2011·Organic Letters·Gary A MolanderValerie A Braz
Aug 5, 2011·The Journal of Organic Chemistry·Gary A Molander, Livia N Cavalcanti
Sep 20, 2011·Organic Letters·Jonathan W LocknerPhil S Baran
Apr 20, 2012·Journal of the American Chemical Society·Alastair J J Lennox, Guy C Lloyd-Jones
Dec 20, 2012·Journal of the American Chemical Society·Tadashi TachinamiHiroshi Naka
Apr 19, 2013·The Journal of Organic Chemistry·Marc PressetGary A Molander
Jun 22, 2013·Nature Chemistry·Karl D Collins, Frank Glorius
Jul 12, 2013·Chemical Communications : Chem Comm·Kazuki MiyazawaMunetaka Akita
Jan 11, 2014·Organic Letters·Stephen D Ramgren, Neil K Garg
Feb 5, 2014·Journal of the American Chemical Society·Hanchu HuangYiyun Chen
Feb 24, 2015·Accounts of Chemical Research·Karl D Collins, Frank Glorius
Sep 16, 2016·Journal of the American Chemical Society·Ming YanPhil S Baran

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Citations

Jan 19, 2019·Organic & Biomolecular Chemistry·Xavier Pannecoucke, Tatiana Besset
Jan 14, 2021·Organic & Biomolecular Chemistry·Maogang RanQiuli Yao
Jun 29, 2021·Organic Letters·Zhihui XuRenhua Qiu
Jul 22, 2021·Chemical Record : an Official Publication of the Chemical Society of Japan ... [et Al.]·José Tiago M CorreiaMárcio W Paixão
Aug 10, 2021·The Journal of Organic Chemistry·Yu-Ming YangZhuangzhu Luo
Aug 28, 2020·The Journal of Organic Chemistry·Juliana A DantasArlene G Corrêa
Oct 2, 2019·Journal of the American Chemical Society·Shasha XieYiyun Chen

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