Electrochemical Azidooxygenation of Alkenes Mediated by a TEMPO-N3 Charge-Transfer Complex

Journal of the American Chemical Society
Juno C SiuSong Lin

Abstract

We report a mild and efficient electrochemical protocol to access a variety of vicinally C-O and C-N difunctionalized compounds from simple alkenes. Detailed mechanistic studies revealed a distinct reaction pathway from those previously reported for TEMPO-mediated reactions. In this mechanism, electrochemically generated oxoammonium ion facilitates the formation of azidyl radical via a charge-transfer complex with azide, TEMPO-N3. DFT calculations together with spectroscopic characterization provided a tentative structural assignment of this charge-transfer complex. Kinetic and kinetic isotopic effect studies revealed that reversible dissociation of TEMPO-N3 into TEMPO• and azidyl precedes the addition of these radicals across the alkene in the rate-determining step. The resulting azidooxygenated product could then be easily manipulated for further synthetic elaborations. The discovery of this new reaction pathway mediated by the TEMPO+/TEMPO• redox couple may expand the scope of aminoxyl radical chemistry in synthetic contexts.

References

Jun 15, 1992·Proceedings of the National Academy of Sciences of the United States of America·M C KrishnaA Russo
Jul 18, 2001·Journal of the American Chemical Society·J SobekH Fischer
Jul 18, 2002·Journal of the American Chemical Society·Amram SamuniPedatsur Neta
Jan 31, 2007·Journal of the American Chemical Society·David J MichaelisTehshik P Yoon
Mar 17, 2007·Journal of the American Chemical Society·Mukund P Sibi, Masayuki Hasegawa
May 10, 2007·The Journal of Organic Chemistry·William F BaileyKenneth B Wiberg
Jun 21, 2008·Chemical Reviews·Jun-ichi YoshidaAiichiro Nagaki
Dec 4, 2008·Journal of the American Chemical Society·Peter H FullerSherry R Chemler
Mar 18, 2010·Journal of the American Chemical Society·Kevin S Williamson, Tehshik P Yoon
Jul 9, 2010·Journal of the American Chemical Society·Jeffrey F Van HumbeckDavid W C MacMillan
May 4, 2011·Angewandte Chemie·Ludger Tebben, Armido Studer
Aug 25, 2011·Journal of the American Chemical Society·Jessica M Hoover, Shannon S Stahl
Jul 27, 2012·Angewandte Chemie·Yi Li, Armido Studer
Jan 16, 2013·Journal of the American Chemical Society·Jessica M HooverShannon S Stahl
Aug 2, 2013·Journal of the American Chemical Society·Teng Wang, Ning Jiao
Aug 13, 2013·Organic Letters·Bo Zhang, Armido Studer
Aug 14, 2013·Chemical Communications : Chem Comm·Yoko HaseKensuke Takechi
Feb 7, 2014·Chemical Society Reviews·Robert Francke, R Daniel Little
Aug 26, 2014·Chemistry : a European Journal·Fan XuHai-Chao Xu
Oct 29, 2014·Journal of the American Chemical Society·David P HickeyShelley D Minteer
Jan 1, 2014·Synlett : Accounts and Rapid Communications in Synthetic Organic Chemistry·Timothy W Liwosz, Sherry R Chemler
Apr 15, 2015·Journal of the American Chemical Society·Xiongyi HuangJohn T Groves
Oct 28, 2015·Journal of the American Chemical Society·Mohammad RafieeShannon S Stahl
Aug 14, 2012·Journal of Chemical Theory and Computation·Björn BaumeierMichael Rohlfing
Nov 26, 2015·Angewandte Chemie·Yong-An YuanHao Xu
May 8, 2012·Journal of Chemical Theory and Computation·Stephan N SteinmannClemence Corminboeuf
Dec 15, 2015·Angewandte Chemie·Fatma TürkyilmazGerhard Erker
Apr 27, 2016·Journal of the American Chemical Society·Brett N HemricQiu Wang
Aug 12, 2017·Science·Niankai FuSong Lin
Sep 19, 2017·Journal of the American Chemical Society·Richard C WalrothKyle M Lancaster
Jan 24, 2018·Angewandte Chemie·Sabine MöhleSiegfried R Waldvogel
Feb 17, 2018·Journal of the American Chemical Society·Markus GriesserDerek A Pratt

❮ Previous
Next ❯

Citations

Feb 7, 2019·Chemical Communications : Chem Comm·Jian ChenLingling Chu
Mar 26, 2020·Angewandte Chemie·Teresa KöselAndreas Kirschning
Dec 15, 2018·Angewandte Chemie·Jin LiGuigen Li
Aug 2, 2019·Chemical Science·Christopher SandfordShelley D Minteer
Jan 23, 2021·Journal of the American Chemical Society·Chisato Wata, Takuya Hashimoto
Jan 16, 2021·The Journal of Organic Chemistry·Vasily D Sen'Victor B Luzhkov
Feb 27, 2021·Chemical Reviews·Paramasivam SivaguruXihe Bi
Dec 30, 2020·Angewandte Chemie·Meng ChenHong Yan
Feb 27, 2021·Chemistry, an Asian Journal·Debabrata MaitiSuman De Sarkar
Jun 2, 2021·Chemical Society Reviews·Luiz F T NovaesSong Lin
Jun 16, 2021·Journal of the American Chemical Society·Nicholas A TillMatthew J Bird
Jun 25, 2021·The Journal of Organic Chemistry·Dian-Liang WangShun-Jun Ji
Jun 25, 2021·Chemical Science·Tjark H MeyerLutz Ackermann
Jul 24, 2021·Journal of the American Chemical Society·Wen LiuXiaoming Feng
Apr 24, 2019·The Journal of Organic Chemistry·Huanliang HongYubing Huang
Sep 10, 2019·Journal of the American Chemical Society·Niankai FuSong Lin
Dec 12, 2019·Accounts of Chemical Research·Cian KingstonPhil S Baran
Nov 23, 2019·Organic Letters·Dodla S RaoSudhir Kashyap
Nov 25, 2020·Journal of the American Chemical Society·Wen Zhang, Song Lin
Jan 24, 2019·Journal of the American Chemical Society·Ju WuGuillaume Vincent
Jan 24, 2019·Journal of the American Chemical Society·Juno C SiuSong Lin
Jun 11, 2019·Journal of the American Chemical Society·Seung Youn Hong, Sukbok Chang
Jul 17, 2019·Journal of the American Chemical Society·Honghui LeiTomislav Rovis

❮ 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.