Efficient cleavage of tertiary amide bonds via radical-polar crossover using a copper(ii) bromide/Selectfluor hybrid system.

Chemical Science
Zhe WangKeiji Maruoka

Abstract

A novel approach for the efficient cleavage of the amide bonds in tertiary amides is reported. Based on the selective radical abstraction of a benzylic hydrogen atom by a CuBr2/Selectfluor hybrid system followed by a selective cleavage of an N-C bond, an acyl fluoride intermediate is formed. This intermediate may then be derivatized in a one-pot fashion. The reaction proceeds under mild conditions and exhibits a broad substrate scope with respect to the tertiary amide moiety as well as to nitrogen, oxygen, and carbon nucleophiles for the subsequent derivatization. Mechanistic studies suggest that the present reaction proceeds via a radical-polar crossover process that involves benzylic carbon radicals generated by the selective radical abstraction of a benzylic hydrogen atom by the CuBr2/Selectfluor hybrid system. Furthermore, a synthetic application of this method for the selective cleavage of peptides is described.

References

Feb 19, 2002·Chemical Reviews·Chryssostomos ChatgilialogluIlhyong Ryu
Dec 4, 2004·Angewandte Chemie·Paul T NyffelerChi-Huey Wong
Apr 13, 2006·Journal of the American Chemical Society·Justin M HoerterShannon S Stahl
Feb 8, 2007·Journal of the American Chemical Society·Denis A KissounkoShannon S Stahl
Dec 21, 2007·Journal of the American Chemical Society·Justin M HoerterShannon S Stahl
Jul 23, 2009·Journal of the American Chemical Society·Nickeisha A StephensonShannon S Stahl
Apr 21, 2011·Journal of Medicinal Chemistry·Stephen D Roughley, Allan M Jordan
Dec 24, 2011·Nature·Vijaya R Pattabiraman, Jeffrey W Bode
Jan 27, 2012·Journal of the American Chemical Society·Quentin MichaudelPhil S Baran
Jun 9, 2012·Organic Letters·Thanh Binh NguyenAli Al-Mourabit
Jun 4, 2013·Drug Discovery Today·Allan A Kaspar, Janice M Reichert
Jan 1, 2011·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Stojan Stavber
Sep 18, 2015·Chemical Society Reviews·Rajeshwer Vanjari, Krishna Nand Singh
May 21, 2016·Nature Communications·Emma L BakerNeil K Garg
Sep 28, 2016·Chemical Reviews·Renata Marcia de FigueiredoJean-Marc Campagne
Nov 5, 2016·Angewandte Chemie·Liana HieNeil K Garg
Jun 1, 2017·Journal of the American Chemical Society·Wen ZhangGuosheng Liu
Jun 9, 2017·Chemistry : a European Journal·Yann Bourne-BranchuGrégory Danoun
Jun 20, 2017·ACS Catalysis·Jacob E Dander, Neil K Garg
Nov 23, 2017·Chemical Science·Jacob E DanderNeil K Garg
Jan 26, 2018·Chemistry : a European Journal·Hongxiang WuZhuo Zeng
Feb 3, 2018·Organic & Biomolecular Chemistry·Yongmei LiuMichal Szostak
Apr 24, 2018·The Journal of Organic Chemistry·Shyam SathyamoorthiRichard N Zare
May 19, 2018·Journal of the American Chemical Society·Chi Wai CheungXile Hu
Sep 6, 2018·Accounts of Chemical Research·Fei WangGuosheng Liu
Sep 21, 2018·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Paola Acosta-GuzmánDiego Gamba-Sánchez
Oct 17, 2018·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Sriram MaheshMonika Raj
Jan 30, 2019·Nature Communications·Linbin NiuAiwen Lei
Feb 16, 2019·Journal of the American Chemical Society·Alexander A VinogradovHiroaki Suga
Apr 10, 2019·Angewandte Chemie·Nicolas Blanchard, Vincent Bizet
Apr 11, 2019·Angewandte Chemie·Yohei Ogiwara, Norio Sakai
Aug 28, 2019·Chemistry : a European Journal·Francisco José Aguilar TroyanoAdrián Gómez-Suárez
Sep 12, 2019·Chemical Record : an Official Publication of the Chemical Society of Japan ... [et Al.]·Kazushi MashimaHaruki Nagae
Dec 14, 2019·Chemical Record : an Official Publication of the Chemical Society of Japan ... [et Al.]·Guangchen Li, Michal Szostak
Mar 4, 2020·Chemistry, an Asian Journal·Zhenhua WangYasushi Nishihara
Jun 17, 2020·Journal of the American Chemical Society·Sung-Eun SuhShannon S Stahl

❮ Previous
Next ❯

Citations

Mar 16, 2021·The Journal of Organic Chemistry·Akira MatsumotoKeiji Maruoka
Jun 29, 2021·The Journal of Organic Chemistry·Alfred K K FungMichelle L Coote

❮ Previous
Next ❯

Methods Mentioned

BETA
NMR

Software Mentioned

Selectfluor

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.