Copper-Catalyzed Electrochemical C-H Amination of Arenes with Secondary Amines

Journal of the American Chemical Society
Qi-Liang YangTian-Sheng Mei

Abstract

Electrochemical oxidation represents an environmentally friendly solution to conventional methods that require caustic stoichiometric chemical oxidants. However, C-H functionalizations merging transition-metal catalysis and electrochemical techniques are, to date, largely confined to the use of precious metals and divided cells. Herein, we report the first examples of copper-catalyzed electrochemical C-H aminations of arenes at room temperature using undivided electrochemical cells, thereby providing a practical solution for the construction of arylamines. The use of n-Bu4NI as a redox mediator is crucial for this transformation. On the basis of mechanistic studies including kinetic profiles, isotope effects, cyclic voltammetric analyses, and radical inhibition experiments, the reaction appears to proceed via a single-electron-transfer (SET) process, and a high valent Cu(III) species is likely involved. These findings provide a new avenue for transition-metal-catalyzed electrochemical C-H functionalization reactions using redox mediators.

References

Mar 30, 1977·Journal of the American Chemical Society·F P BossuD W Margerum
Sep 25, 2003·Journal of the American Chemical Society·Hiromitsu MaedaHiroyuki Furuta
May 20, 2006·Nature Chemical Biology·Ryan Hili, Andrei K Yudin
May 25, 2006·Journal of the American Chemical Society·Xiao ChenJin-Quan Yu
Jun 23, 2006·Chemical Society Reviews·Jeffrey B Sperry, Dennis L Wright
Jun 21, 2008·Chemical Reviews·Jun-ichi YoshidaAiichiro Nagaki
Jun 28, 2008·Journal of the American Chemical Society·Lauren M Huffman, Shannon S Stahl
Jul 9, 2008·Chemical Reviews·Anny Jutand
Aug 14, 2008·Accounts of Chemical Research·Dawei Ma, Qian Cai
Dec 17, 2008·Journal of the American Chemical Society·Eric R StrieterStephen L Buchwald
Mar 21, 2009·Science·Robert J Phipps, Matthew J Gaunt
Jun 26, 2009·Accounts of Chemical Research·Olafs DaugulisDmitry Shabashov
Jul 10, 2009·Chemical Communications : Chem Comm·Alexis Perry, Richard J K Taylor
Jul 30, 2009·Journal of the American Chemical Society·Fumitoshi KakiuchiTakamasa Tanabe
Aug 8, 2009·Chemical Communications : Chem Comm·Keith M Gligorich, Matthew S Sigman
Jan 19, 2010·Angewandte Chemie·Masayuki WasaJin-Quan Yu
Mar 13, 2010·Organic Letters·Jayasree SeayadChristina L L Chai
Jul 31, 2010·Organic Letters·Johannes E M N KleinRichard J K Taylor
Aug 10, 2010·Journal of the American Chemical Society·Amanda E KingShannon S Stahl
Jan 15, 2011·Chemical Society Reviews·Florence ColletPhilippe Dauban
Mar 16, 2011·The Journal of Organic Chemistry·Alex John, Kenneth M Nicholas
Apr 28, 2011·Journal of the American Chemical Society·Bo ChenYun-Dong Wu
Oct 29, 2011·Angewandte Chemie·Alison E WendlandtShannon S Stahl
Jan 1, 2010·Chemical Science·David S Surry, Stephen L Buchwald
Jan 1, 2011·Chemical Science·David S Surry, Stephen L Buchwald
Apr 14, 2012·Nature·Amanda J Hickman, Melanie S Sanford
May 2, 2012·Accounts of Chemical Research·Jennifer L RoizenJ Du Bois
Aug 14, 2012·The Journal of Organic Chemistry·Hiroko AisoFumitoshi Kakiuchi
Oct 4, 2012·Organic Letters·Stephen Sanjaya, Shunsuke Chiba
Apr 26, 2013·Angewandte Chemie·Ly Dieu TranOlafs Daugulis
Jun 12, 2013·Journal of the American Chemical Society·Alison M SuessShannon S Stahl
Nov 12, 2013·Chemical Communications : Chem Comm·Vedhagiri S ThirunavukkarasuLutz Ackermann
Nov 13, 2013·Chemical Society Reviews·Marie-Laure Louillat, Frederic W Patureau
Jan 23, 2014·Journal of the American Chemical Society·Hien-Quang DoGregory C Fu
Feb 4, 2014·Chemical Communications : Chem Comm·Ángel Manu MartínezJuan C Carretero
Feb 7, 2014·Chemical Society Reviews·Robert Francke, R Daniel Little
Feb 18, 2014·Journal of the American Chemical Society·Ming ShangJin-Quan Yu
Mar 4, 2014·Chemical Society Reviews·Carlo SambiagioPatrick C McGowan
Apr 17, 2014·The Journal of Organic Chemistry·Hui XuZengming Shen

❮ Previous
Next ❯

Citations

Oct 24, 2018·Chemical Communications : Chem Comm·Guanyinsheng QiuJie Wu
Nov 1, 2018·Chemistry : a European Journal·Shou-Kun ZhangLutz Ackermann
Jan 24, 2019·Chemical Communications : Chem Comm·Yi YuAiwen Lei
Mar 23, 2019·Chemical Communications : Chem Comm·Yong YuanAiwen Lei
Oct 19, 2019·Angewandte Chemie·Jin-Feng YuJin-Quan Yu
Jan 9, 2020·Chemical Communications : Chem Comm·Ruhuai MeiLutz Ackermann
Dec 26, 2019·Chemistry : a European Journal·Youai QiuLutz Ackermann
Mar 21, 2020·Chemical Communications : Chem Comm·Mingxiang ZhuSamir Messaoudi
Feb 12, 2020·Chemistry : a European Journal·Yongqi YaoDingqiao Yang
Apr 24, 2020·Angewandte Chemie·Ramesh C SamantaLutz Ackermann
Apr 30, 2020·Angewandte Chemie·Yan ZhangLutz Ackermann
May 28, 2020·Chemical Society Reviews·Parthasarathy GandeepanLutz Ackermann
Jul 24, 2020·Organic & Biomolecular Chemistry·Huanliang HongYubing Huang
Dec 15, 2018·Angewandte Chemie·Jin LiGuigen Li
Apr 16, 2019·Nature Catalysis·Lei ZhangXile Hu
Aug 2, 2019·Chemical Science·Christopher SandfordShelley D Minteer
Dec 1, 2019·Nature Communications·Xia HuAiwen Lei
Apr 3, 2020·Topics in Current Chemistry·Yafeng YangEsmail Vessally
Nov 3, 2020·Organic & Biomolecular Chemistry·Partha Pratim SenSudipta Raha Roy
Oct 22, 2020·Chemistry : a European Journal·Yan ZhangLutz Ackermann

❮ Previous
Next ❯

Related Concepts

Trending Feeds

COVID-19

Coronaviruses encompass a large family of viruses that cause the common cold as well as more serious diseases, such as the ongoing outbreak of coronavirus disease 2019 (COVID-19; formally known as 2019-nCoV). Coronaviruses can spread from animals to humans; symptoms include fever, cough, shortness of breath, and breathing difficulties; in more severe cases, infection can lead to death. This feed covers recent research on COVID-19.

Blastomycosis

Blastomycosis fungal infections spread through inhaling Blastomyces dermatitidis spores. Discover the latest research on blastomycosis fungal infections here.

Nuclear Pore Complex in ALS/FTD

Alterations in nucleocytoplasmic transport, controlled by the nuclear pore complex, may be involved in the pathomechanism underlying multiple neurodegenerative diseases including Amyotrophic Lateral Sclerosis and Frontotemporal Dementia. Here is the latest research on the nuclear pore complex in ALS and FTD.

Applications of Molecular Barcoding

The concept of molecular barcoding is that each original DNA or RNA molecule is attached to a unique sequence barcode. Sequence reads having different barcodes represent different original molecules, while sequence reads having the same barcode are results of PCR duplication from one original molecule. Discover the latest research on molecular barcoding here.

Chronic Fatigue Syndrome

Chronic fatigue syndrome is a disease characterized by unexplained disabling fatigue; the pathology of which is incompletely understood. Discover the latest research on chronic fatigue syndrome here.

Evolution of Pluripotency

Pluripotency refers to the ability of a cell to develop into three primary germ cell layers of the embryo. This feed focuses on the mechanisms that underlie the evolution of pluripotency. Here is the latest research.

Position Effect Variegation

Position Effect Variagation occurs when a gene is inactivated due to its positioning near heterochromatic regions within a chromosome. Discover the latest research on Position Effect Variagation here.

STING Receptor Agonists

Stimulator of IFN genes (STING) are a group of transmembrane proteins that are involved in the induction of type I interferon that is important in the innate immune response. The stimulation of STING has been an active area of research in the treatment of cancer and infectious diseases. Here is the latest research on STING receptor agonists.

Microbicide

Microbicides are products that can be applied to vaginal or rectal mucosal surfaces with the goal of preventing, or at least significantly reducing, the transmission of sexually transmitted infections. Here is the latest research on microbicides.