Abstract
Site selective chemical functionalization at unactivated C(sp3)-H bonds is highly challenging and recent successful studies mostly focus on the use of transition metal catalysis in combination with directing groups. Radical chemistry offers a complementary approach with the Barton and the Hofmann-Löffler-Freytag reactions being landmark contributions in the area of remote C-H functionalization at unactivated aliphatic sites. Herein we introduce the concept of radical translocation arylation at unactivated secondary and tertiary C(sp3)-H bonds in various alcohols. The straightforward two-step sequence comprises an ionic alcohol sulfonylation with especially designed ortho-iodoaryl sulfonyl chlorides followed by a radical cascade reaction including aryl radical generation, remote radical translocation, aryl migration, reduction, and SO2 extrusion to give the corresponding γ-arylated alcohols. Moderate to good yields are obtained, remote C-H arylation occurs with excellent regioselectivity and for secondary C(sp3)-H bonds good to excellent stereoselectivity is achieved.
References
Nov 12, 1975·Journal of the American Chemical Society·E J Corey, H E Ensley
Jul 25, 2012·Nature Chemistry·Ana-Florina VoicaPhil S Baran
Aug 14, 2012·Angewandte Chemie·Junichiro YamaguchiKenichiro Itami
Mar 11, 2015·Accounts of Chemical Research·Olafs DaugulisLy Dieu Tran
May 9, 2015·Chemical Society Reviews·Zhi-Min ChenYong-Qiang Tu
Feb 18, 2016·Nature·Joseph J TopczewskiMelanie S Sanford
Oct 5, 2016·Science·Gang ChenJin-Quan Yu
Nov 4, 2016·Nature·John C K Chu, Tomislav Rovis
Nov 4, 2016·Nature·Gilbert J ChoiRobert R Knowles
Feb 6, 2017·Science·Qing-Feng WuJin-Quan Yu
Jul 13, 2017·Chemical Reviews·Jian HeJin-Quan Yu
Nov 28, 2017·Chemical Society Reviews·Weipeng LiChengjian Zhu
Dec 26, 2017·Angewandte Chemie·Xinxin WuChen Zhu
Feb 17, 2018·Science·Tyler G Saint-DenisJin-Quan Yu
May 15, 2018·Synthesis·Leah M StatemanDavid A Nagib
Citations
Dec 5, 2018·Angewandte Chemie·Shuo WuChen Zhu
Feb 17, 2019·Nature Communications·Xu BaoJieping Zhu
Dec 14, 2019·Nature Communications·Zhen-Hua ZhangXin-Yuan Liu
Dec 15, 2020·Chemical Society Reviews·Nikita Kvasovs, Vladimir Gevorgyan
Nov 21, 2020·Angewandte Chemie·Niklas Radhoff, Armido Studer
Sep 9, 2020·Angewandte Chemie·Enzo NobileTatiana Besset
Jan 23, 2021·Chemistry : a European Journal·Oliver Fischer, Markus R Heinrich
May 14, 2021·Organic Letters·Qu-Ping HuFei Pan
Jun 22, 2021·Journal of the American Chemical Society·Dinghai WangArmido Studer
Jun 15, 2021·Chemical Science·Sumon SarkarVladimir Gevorgyan
Jun 12, 2019·Organic Letters·Shan YangChen Zhu
May 3, 2019·Journal of the American Chemical Society·Daria KurandinaVladimir Gevorgyan
Jun 30, 2019·Organic Letters·Huiqiao WangKun Xu
Nov 2, 2019·Organic Letters·Chuanyong WangWei-Liang Duan
Jan 7, 2020·Organic Letters·Lisa-Marie AltmannMarkus R Heinrich
Jun 13, 2019·Organic Letters·Yimei WanGangguo Zhu
Jul 25, 2020·Accounts of Chemical Research·Xinxin Wu, Chen Zhu
Aug 10, 2021·Angewandte Chemie·David M WhalleyMichael F Greaney
Nov 12, 2021·Journal of the American Chemical Society·Juanjuan WangXuebo Chen
Jan 26, 2022·Chemical Communications : Chem Comm·Qu-Ping HuFei Pan