Two-step conversion of carboxylic esters into distally fluorinated ketones via ring cleavage of cyclopropanol intermediates: application of sulfinate salts as fluoroalkylating reagents

Organic & Biomolecular Chemistry
Yulia A KonikDzmitry G Kananovich

Abstract

Tertiary cyclopropanols easily available from carboxylic esters have been used in the synthesis of distally fluorinated ketones. Cyclopropane ring cleavage reactions in methanol with aqueous tert-butyl hydroperoxide in the presence of a copper(ii) acetate catalyst and sodium triflinate (Langlois reagent) afford β-trifluoromethyl ketones in 16-74% isolated yields. Sodium triflinate serves as a precursor of reactive trifluoromethyl copper species, enabling ring-opening trifluoromethylation, as evidenced by mechanistic studies. We also demonstrate here that other sulfinate salts, such as sodium 1,1-difluoroethanesulfinate, sodium 2-(4-bromophenyl)-1,1-difluoroethanesulfinate and sodium 1-(trifluoromethyl)cyclopropanesulfinate, can be used as fluoroalkylation reagents, resulting in the corresponding fluorinated ketones.

References

Jul 10, 2003·Chemical Reviews·Oleg G Kulinkovich
Apr 5, 2011·Chemical Reviews·Olesya A Tomashenko, Vladimir V Grushin
Dec 6, 2011·Journal of the American Chemical Society·Alessandro ZanardiVladimir V Grushin
Dec 24, 2011·Journal of the American Chemical Society·Xin MuGuosheng Liu
Aug 14, 2012·Organic & Biomolecular Chemistry·Isabell Haym, Margaret A Brimble
Sep 25, 2012·Journal of the American Chemical Society·Petr NovákVladimir V Grushin
Apr 5, 2013·Chemical Communications : Chem Comm·Shangjun CaiChanjuan Xi
Jul 13, 2013·Chemical Communications : Chem Comm·Hiromichi EgamiMikiko Sodeoka
Nov 28, 2013·The Journal of Organic Chemistry·Tatiana BessetXavier Pannecoucke
Dec 7, 2013·Chemical Communications : Chem Comm·Tang-Po YangJi-Chang Xiao
Dec 25, 2013·Beilstein Journal of Organic Chemistry·Grégory LandelleFrédéric R Leroux
Aug 5, 2014·Angewandte Chemie·Ryan GianatassioPhil S Baran
Aug 26, 2014·Chemical Reviews·Julie CharpentierAntonio Togni
Nov 26, 2014·Journal of the American Chemical Society·Noel Nebra, Vladimir V Grushin
Jan 22, 2015·Angewandte Chemie·Andrew M RomineVladimir V Grushin
Jan 31, 2015·Chemical Reviews·Concepción AlonsoFrancisco Palacios
Mar 4, 2015·Journal of the American Chemical Society·Huijun ZhaoChen Zhu
Mar 5, 2015·Chemistry : a European Journal·Pin GaoYong-Min Liang
Apr 14, 2015·Organic & Biomolecular Chemistry·Shichao RenTeck-Peng Loh
Apr 17, 2015·Chemistry : a European Journal·Steven BloomThomas Lectka
Jun 13, 2015·Organic & Biomolecular Chemistry·Xia-Ping HeHua-Jian Xu
Nov 4, 2015·Chemistry : a European Journal·William DolbierZuxiao Zhang
Dec 23, 2015·Chemistry : a European Journal·Yuwen ZengJinbo Hu
Jun 30, 2016·Organic & Biomolecular Chemistry·Sebastian Barata-VallejoAl Postigo
Sep 17, 2016·Journal of the American Chemical Society·Samuel Martinez-ErroBelén Martín-Matute

❮ Previous
Next ❯

Citations

Feb 26, 2019·Beilstein Journal of Organic Chemistry·Yu LiuQuan Zhou
May 5, 2020·Organic & Biomolecular Chemistry·Xiaobao ZengYu Zhao
Sep 25, 2017·Organic & Biomolecular Chemistry·Yulia A KonikDzmitry G Kananovich
Mar 1, 2018·Chemical Communications : Chem Comm·Maryia V BarysevichVladimir A Khripach
Jan 16, 2021·Angewandte Chemie·Ming-Ming Wang, Jérôme Waser
Oct 22, 2020·Chemical Reviews·Tyler R McDonaldSophie A L Rousseaux
Oct 19, 2019·Organic Letters·L Reginald MillsSophie A L Rousseaux
Jun 14, 2017·Organic Letters·Gábor Zoltán ElekDzmitry G Kananovich

❮ 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.