Remote C-H functionalization using radical translocating arylating groups

Nature Communications
Florian W FrieseArmido Studer

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
Jul 13, 2017·Chemical Reviews·Jian HeJin-Quan Yu
Nov 28, 2017·Chemical Society Reviews·Weipeng LiChengjian Zhu
May 15, 2018·Synthesis·Leah M StatemanDavid A Nagib

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Citations

Dec 15, 2020·Chemical Society Reviews·Nikita Kvasovs, Vladimir Gevorgyan
Jan 23, 2021·Chemistry : a European Journal·Oliver Fischer, Markus R Heinrich
Jun 22, 2021·Journal of the American Chemical Society·Dinghai WangArmido Studer
May 3, 2019·Journal of the American Chemical Society·Daria KurandinaVladimir Gevorgyan
Jan 7, 2020·Organic Letters·Lisa-Marie AltmannMarkus R Heinrich
Jul 25, 2020·Accounts of Chemical Research·Xinxin Wu, Chen Zhu
Jan 26, 2022·Chemical Communications : Chem Comm·Qu-Ping HuFei Pan

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