Fundamental studies and development of nickel-catalyzed trifluoromethylthiolation of aryl chlorides: active catalytic species and key roles of ligand and traceless MeCN additive revealed

Journal of the American Chemical Society
Guoyin YinFranziska Schoenebeck

Abstract

A catalytic protocol to convert aryl and heteroaryl chlorides to the corresponding trifluoromethyl sulfides is reported herein. It relies on a relatively inexpensive Ni(cod)2/dppf (cod = 1,5-cyclooctadiene; dppf = 1,1'-bis(diphenylphosphino)ferrocene) catalyst system and the readily accessible coupling reagent (Me4N)SCF3. Our computational and experimental mechanistic data are consistent with a Ni(0)/Ni(II) cycle and inconsistent with Ni(I) as the reactive species. The relevant intermediates were prepared, characterized by X-ray crystallography, and tested for their catalytic competence. This revealed that a monomeric tricoordinate Ni(I) complex is favored for dppf and Cl whose role was unambiguously assigned as being an off-cycle catalyst deactivation product. Only bidentate ligands with wide bite angles (e.g., dppf) are effective. These bulky ligands render the catalyst resting state as [(P-P)Ni(cod)]. The latter is more reactive than Ni(P-P)2, which was found to be the resting state for ligands with smaller bite angles and suffers from an initial high-energy dissociation of one ligand prior to oxidative addition, rendering the system unreactive. The key to effective catalysis is hence the presence of a labile auxiliary ligan...Continue Reading

References

Sep 1, 1975·Journal of Medicinal Chemistry·A LeoC Hansch
Jul 18, 2001·Journal of the American Chemical Society·D J Mindiola, G L Hillhouse
Aug 9, 2002·Journal of the American Chemical Society·Juventino J GarciaWilliam D Jones
Nov 28, 2002·Journal of the American Chemical Society·Patrick L HollandRene J Lachicotte
Jan 16, 2004·Organic Letters·Chaya PooputWilliam R Dolbier
Jul 1, 2004·Journal of the American Chemical Society·Thomas J AndersonDavid A Vicic
Jan 13, 2005·Journal of the American Chemical Society·David A PowellGregory C Fu
Mar 10, 2005·Chemical Reviews·Frédéric LerouxManfred Schlosser
Aug 16, 2005·Chemical Communications : Chem Comm·Gavin D JonesDavid A Vicic
Feb 16, 2006·Journal of the American Chemical Society·Manuel A Fernández-RodríguezJohn F Hartwig
Sep 30, 2006·Chemistry : a European Journal·Manuel A Fernández-RodríguezJohn F Hartwig
Oct 5, 2006·Journal of the American Chemical Society·Gavin D JonesDavid A Vicic
Sep 6, 2008·The Journal of Organic Chemistry·Kyrill StanekAntonio Togni
Feb 26, 2009·Organic Letters·Kyoungsoo LeeJames P Stambuli
Mar 19, 2009·Journal of the American Chemical Society·Jorge Torres-NietoJuventino J García
May 8, 2009·Chemical Society Reviews·Mandy-Nicole BirkholzPiet W N M van Leeuwen
Jun 19, 2010·Chemical Communications : Chem Comm·Caroline J E DaviesMichael K Whittlesey
Aug 10, 2010·Journal of the American Chemical Society·Vlad M Iluc, Gregory L Hillhouse
Sep 21, 2010·Accounts of Chemical Research·Da-Gang YuZhang-Jie Shi
Nov 12, 2010·Accounts of Chemical Research·Sebastian Kozuch, Sason Shaik
Dec 8, 2010·Chemical Reviews·Brad M RosenVirgil Percec
Jan 19, 2011·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Chad C Eichman, James P Stambuli
Apr 5, 2011·Journal of the American Chemical Society·Kyle W QuasdorfNeil K Garg
Apr 7, 2011·The Journal of Organic Chemistry·Nico Santschi, Antonio Togni
May 17, 2011·Organometallics·Kainan ZhangJanis Louie
Jun 22, 2011·Angewandte Chemie·Georgiy TeverovskiyStephen L Buchwald
Sep 20, 2011·Chemistry : a European Journal·Philipp Anstaett, Franziska Schoenebeck
Oct 26, 2011·Journal of the American Chemical Society·Mamoru TobisuNaoto Chatani
Dec 14, 2011·Journal of the American Chemical Society·Cheng-Pan Zhang, David A Vicic
Jan 20, 2012·Organic Letters·Nekane Barbero, Ruben Martin
Feb 18, 2012·Organic Letters·Andrew R EhleMary P Watson
Mar 1, 2012·Chemistry : a European Journal·Zhe LiYao Fu
May 11, 2012·Angewandte Chemie·Carin C C Johansson SeechurnVictor Snieckus
May 29, 2012·Chemistry, an Asian Journal·Cheng-Pan Zhang, David A Vicic

❮ Previous
Next ❯

Citations

Feb 18, 2016·Journal of the American Chemical Society·Long Xu, David A Vicic
Jul 15, 2015·Organic Letters·Yi-Feng QiuYong-Min Liang
May 14, 2016·Accounts of Chemical Research·Theresa SpergerFranziska Schoenebeck
Oct 1, 2016·Journal of the American Chemical Society·Nicholas D StaudaherJanis Louie
Dec 24, 2016·Journal of the American Chemical Society·Megan Mohadjer BeromiDavid J Vinyard
Feb 18, 2016·Chemistry : a European Journal·Roman HonekerFrank Glorius
Mar 28, 2016·Chemistry : a European Journal·Keywan A JohnsonDaniel J Weix
Jul 5, 2017·Chemical Society Reviews·Chun-Yi Lin, Philip P Power
Feb 1, 2016·Chemical Science·Alexander B DürrFranziska Schoenebeck
Jun 16, 2015·Dalton Transactions : an International Journal of Inorganic Chemistry·S YuD A Vicic
Aug 30, 2017·Chemical Communications : Chem Comm·Huan LiFeng-Ling Qing
May 12, 2018·Chemistry : a European Journal·Paul H GehrtzIvana Fleischer
Dec 22, 2017·Chemistry, an Asian Journal·Zhen-Yu WangXi-Sheng Wang
Oct 24, 2018·Dalton Transactions : an International Journal of Inorganic Chemistry·Ailing ZhangWenguang Wang
Apr 2, 2019·Chemical Communications : Chem Comm·Perumal Saravanan, Pazhamalai Anbarasan
May 3, 2019·Angewandte Chemie·Yong Xia, Armido Studer
Dec 13, 2019·Angewandte Chemie·Tristan DelcaillauBill Morandi
Jan 19, 2020·Chemistry : a European Journal·David D DawsonElizabeth R Jarvo
Jul 16, 2020·Angewandte Chemie·Sary Abou DerhamineAbderrahmane Amgoune
Jul 6, 2016·Chemistry : a European Journal·Christian MatheisLukas J Goossen
Oct 23, 2018·Angewandte Chemie·Theresa SpergerFranziska Schoenebeck
Jan 11, 2019·Chemical Science·Feng WangPingping Tang
Dec 6, 2017·Chemistry : a European Journal·Thomas ScattolinFranziska Schoenebeck

❮ 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.