- A convenient method for the transformation of alcohols into alkyl trifluoromethyl sulfides
-
Alkyl trifluoromethyl sulfides are prepared by phosphitylation of alcohols or α-hydroxy esters using bis(diethylamido)chlorophosphite followed by the reaction with bis(trifluoromethyl) disulfide under extremely mild conditions in near by quantitative yields.
- Kolomeitsev,Chabanenko,Roschenthaler,Yagupolskii
-
-
Read Online
- A new simple access to trifluoromethyl thioethers or selenoethers from trifluoromethyl trimethylsilane and disulfides or diselenides
-
Trifluoromethyl thioethers (or selenoethers) are easily obtained in one pot at 0°C from disulfides (or diselenides), commercial trifluoromethyl trimethyl silane and TBAF.
- Billard, Thierry,Langlois, Bernard R.
-
-
Read Online
- Trifluoromethyl Sulfoxides: Reagents for Metal-Free C?H Trifluoromethylthiolation
-
Trifluoromethyl sulfoxides are a new class of trifluoromethylthiolating reagent. The sulfoxides engage in metal-free C?H trifluoromethylthiolation with a range of (hetero)arenes. The method is also applicable to the functionalization of important compound classes, such as ligand derivatives and polyaromatics, and in the late-stage trifluoromethylthiolation of medicines and agrochemicals. The isolation and characterization of a sulfonium salt intermediate supports an interrupted Pummerer reaction mechanism.
- Carlton, C. Grace,McDouall, Joseph J. W.,Perry, Gregory J. P.,Procter, David J.,Tayu, Masanori,Wang, Dong
-
supporting information
p. 15918 - 15922
(2020/07/20)
-
- The First Organosilver(III) Fluoride, [PPh4][(CF3)3AgF]
-
Organosilver(III) fluoride complexes have been assigned a key role in different fluorination processes. To the best of our knowledge, however, none of them seem to have been isolated or even detected thus far. Here we report on the successful synthesis of the trifluoromethyl derivative [PPh4][(CF3)3AgF], which has been isolated in high yield. The thermodynamic stability of the Ag?F bond is shown by calculation and demonstrated by multistage mass spectrometry (MSn) under collision-induced dissociation (CID) conditions. Nevertheless, the substantial elongation found in the Ag?F bond (X-ray) is correlated with a marked nucleophilic character of the terminal F ligand. This Ag?F bond is, in fact, quite reactive: it suffers hydrolysis and is also solvolyzed by thiols.
- Joven-Sancho, Daniel,Baya, Miguel,Martín, Antonio,Orduna, Jesús,Menjón, Babil
-
supporting information
p. 4471 - 4475
(2020/02/27)
-
- Fluoroalkylselenolation of Alkyl Silanes/Trifluoroborates under Metal-Free Visible-Light Photoredox Catalysis
-
Herein a metal-free fluoroalkylselenolation of alkylsilanes as well as potassium alkyltrifluoroborates under visible light photocatalysis is disclosed. The developed methodologies are performed under mild conditions, room temperature in the presence of an organic photocatalyst and blue LED irradiation. Mechanistic investigations including luminescence and EPR spectroscopy allow us to shed light on both mechanisms.
- Ghiazza, Clément,Khrouz, Lhoussain,Billard, Thierry,Monnereau, Cyrille,Tlili, Anis
-
supporting information
p. 1559 - 1566
(2019/11/03)
-
- MANUFACTURING METHOD OF FLUORINE-CONTAINING METHYLTHIO SUBSTITUTED COMPOUND
-
PROBLEM TO BE SOLVED: To provide a manufacturing method of a fluorine-containing methylthio substituted compound using a novel fluorine-containing methylthio group introduction agent. SOLUTION: A fluorine-containing methylthio introduction agent consistin
- -
-
Paragraph 0036-0038; 0039-0041
(2019/12/25)
-
- Ir(III)-Catalyzed mono-olefination of Aryl C-H Bonds Using -SCF3 as a Weak directing group
-
The trifluoromethylthionyl group (-SCF3) is an efficient weak directing group for Ir(III)-catalyzed aryl C-H olefination. Various trifluoromethylthioethers provide high levels of mono-olefination products in good to excellent yields under mild conditions with a 2,2′-bipyridine ligand or AgBF4 as an additive. Mechanistic studies indicate the C-H cleavage is the rate-determining step. The directing group ability of the -SCF3 group is benchmarked against several other weak directing groups by competition experiments under Ir(III)-catalyzed conditions.
- Bao, Rui-Peng,Chen, Xian,Li, Chen,Wang, Dong-Hui
-
supporting information
p. 8116 - 8121
(2019/10/14)
-
- COMPLEXES FOR NUCLEOPHILIC, RADICAL, AND ELECTROPHILIC POLYFLUOROALKYLATION
-
Disclosed herein are borazine complexes and use of the same in perfluoroalkylation reactions.
- -
-
Paragraph 00135
(2018/04/11)
-
- Metal-Free Direct Dehydroxytrifluoromethylthiolation of Alcohols via the Umpolung Reactivity of Trifluoromethanesulfenamides
-
A direct dehydroxytrifluoromethylthiolation of alcohols with trifluoromethanesulfenamide has been described. This method, based on the original umpolung reactivity of trifluoromethanesulfenamides, proposes a direct "OH-SCF3 exchange" under mild and, more especially, metal-free conditions.
- Glenadel, Quentin,Tlili, Anis,Billard, Thierry
-
supporting information
p. 1955 - 1957
(2016/04/26)
-
- Trifluoromethylation of thiophenols and thiols with sodium trifluoromethanesulfinate and iodine pentoxide
-
A selective and facile trifluoromethylation process for a wide range of thiophenols and thiols under metal free conditions has been developed using two simple and safe solids, sodium trifluoro-methanesulfinate and iodine pentoxide, via the radical process.
- Ma, Jing-Jing,Yi, Wen-Bin,Lu, Guo-Ping,Cai, Chun
-
p. 417 - 421
(2016/02/03)
-
- Preparation of difluoromethylthioethers through difluoromethylation of disulfides using TMS-CF2H
-
We report an operationally simple, metal-free approach for the late-stage introduction of the important lipophilic hydrogen-bond donor motif, SCF2H. This reaction converts diaryl- and dialkyl-disulfides into the corresponding aryl/alkyl-SCF2H through the nucleophilic transfer of a difluoromethyl group with good functional group tolerance. This method is notable for its use of commercially available TMSCF2H, and does not rely on the need for handling of sensitive metal complexes.
- Howard, Joseph L.,Schotten, Christiane,Alston, Stephen T.,Browne, Duncan L.
-
supporting information
p. 8448 - 8451
(2016/07/07)
-
- First and second generation of trifluoromethanesulfenamide reagent: A trifluoromethylthiolating comparison
-
Trifluoromethylthiolation of molecules is a more and more studied reaction. In particular, the direct electrophilic trifluoromethylthiolation plays an important role in this chemistry. Among the various developed reagents, trifluoromethanesulfenamides constitute an efficient family of reagents. However, no systematic comparison of these two generations has been realized. In this paper, the difference of reactivity of these reagents is studied towards various nucleophiles.
- Glenadel, Quentin,Alazet, Sébastien,Billard, Thierry
-
-
- Metal-Free Trifluoromethylthiolation of Alkyl Electrophiles via a Cascade of Thiocyanation and Nucleophilic Cyanide-CF3 Substitution
-
A straightforward synthesis of alkyl trifluoromethyl thioethers was developed that starts from widely available alkyl halides or mesylates and the inexpensive reagents sodium thiocyanate and trimethyl(trifluoromethyl)silane. The alkyl electrophiles are converted in situ into the corresponding thiocyanates, which react with the nucleophilic Ruppert-Prakash reagent to give the corresponding trifluoromethyl thioethers via a Langlois-type CN-CF3 substitution. This process enables the efficient introduction of the pharmaceutically meaningful trifluoromethylthio groups into functionalized molecules without the need of metal catalysts or expensive preformed trifluoromethylthiolating agents.
- Matheis, Christian,Wang, Minyan,Krause, Thilo,Goossen, Lukas J.
-
supporting information
p. 1628 - 1632
(2015/06/30)
-
- An efficient and practical approach to trifluoromethylthiolation of α-haloketones/α-haloarylmethanes
-
An efficient and practical approach to trifluoromethylthiolation of α-haloketones/α-haloarylmethanes was developed. The transformation employs only AgSCF3 and KI in situ generated active nucleophilic trifluoromethylthio species and cleanly occurs in up to quantitative yield at room temperature, thereby providing an unprecedentedly easy entry to various α-SCF3-substituted ketones/arylmethanes.
- Jiang, Min,Zhu, Fangxia,Xiang, Haoyue,Xu, Xing,Deng, Lianfu,Yang, Chunhao
-
p. 6935 - 6939
(2015/06/25)
-
- A mild and fast photocatalytic trifluoromethylation of thiols in batch and continuous-flow
-
S-CF3 bonds are important structural motifs in various pharmaceutical and agrochemical compounds. However, their preparation remains a major challenge in synthetic organic chemistry. Here, we report the development of a mild and fast photocatalytic trifluoromethylation of thiols. The combination of commercially available Ru(bpy)3Cl2, visible light and inexpensive CF3I gas proved to be an efficient method for the direct trifluoromethylation of thiols. The protocol is demonstrated on a wide range of aromatic, hetero-aromatic and aliphatic substrates in both batch and continuous microflow (32 examples, 52-98% yield). Process intensification through continuous microflow application resulted in a 15-fold increase in production rate (0.25 mmol min-1) due to improved gas-liquid mass transfer, enhanced irradiation as well as convenient handling of the gaseous CF3 source. Furthermore, the efficiency of the flow process allowed to reduce the amount of CF3I (1.1 equivalent) to reach full conversion. This journal is
- Straathof, Natan J. W.,Tegelbeckers, Bart J. P.,Hessel, Volker,Wang, Xiao,Nol, Timothy
-
p. 4768 - 4773
(2015/01/09)
-
- Copper-catalyzed direct trifluoromethylthiolation of benzylic C-H bonds via nondirected oxidative C(sp3)-H activation
-
A copper-catalyzed trifluoromethylthiolation of benzylic sp3 C-H bonds was developed via nondirected oxidative C-H activation using readily prepared and stable AgSCF3. This reaction provides a novel and straightforward method for the preparation of various benzyl trifluoromethyl sulfides.
- Chen, Chao,Xu, Xiu-Hua,Yang, Bin,Qing, Feng-Ling
-
supporting information
p. 3372 - 3375
(2014/07/08)
-
- Room temperature nucleophilic trifluoromethylthiolation of benzyl bromides with (bpy)Cu(SCF3)
-
The nucleophilic trifluoromethylthiolation of benzyl bromides using (bpy)Cu(SCF3) gave the desired products of benzyl trifluoromethyl sulfides in good to excellent yields. A diverse set of important functional groups including cyano, nitro, ester, alkoxy, halide, and heterocyclic groups can be well tolerated in the protocol.
- Kong, Dedao,Jiang, Zhou,Xin, Shaogang,Bai, Zhengshuai,Yuan, Yaofeng,Weng, Zhiqiang
-
p. 6046 - 6050
(2013/07/27)
-
- Electrophilic trifluoromethanesulfanylation of organometallic species with trifluoromethanesulfanamides
-
It's so easy. Direct trifluoromethanesulfanylation reactions remain difficult to perform because of the lack of reagents that are stable and easy to handle. Trifluoromethanesulfanamides are reagents which, in combination with readily available Grignard re
- Baert, Francois,Colomb, Julie,Billard, Thierry
-
supporting information
p. 10382 - 10385,4
(2012/12/11)
-
- Decoupling deprotonation from metalation: Thia-fries rearrangement
-
(Chemical Equation Presented) Label-enabled: Studies with 2H-, 18O-, and 34S-labeled aryl triflates show that lithium diisopropylamide-mediated thia-Fries rearrangement proceeds through an irreversible ortho deprotonation (see scheme; DIPA = diisopropylamine, LDA = lithium diisopropylamide). In contrast, ortho metalation results exclusively in the generation of a benzyne.
- Dyke, Alan M.,Gill, Duncan M.,Harvey, Jeremy N.,Hester, Alison J.,Lloyd-Jones, Guy C.,Munoz, M. Paz,Shepperson, Ian R.
-
supporting information; experimental part
p. 5067 - 5070
(2009/03/11)
-
- A new preparation of trifluoromethanesulfinate salts
-
Trifluoromethanesulfinate (triflinate) salts can be prepared in an ecofriendly way by β-elimination of aliphatic triflones bearing an acidic hydrogen in β position. This technique allows the synthesis of various triflinate salts under mild conditions.
- Langlois, Bernard R.,Billard, Thierry,Mulatier, Jean-Christophe,Yezeguelian, Catherine
-
p. 851 - 856
(2008/03/13)
-
- Selective aliphatic fluorination by halogen exchange in mild conditions
-
HF-Base media, in particular (HF)10-pyridine or (HF) 3-triethylamine, allow aliphatic chlorine-fluorine exchanges on acid-sensitive molecules. Depending on the nature (pyridine or triethylamine), stoichiometry of the base and temperature, selective mono-, di-, or tri-chlorine-fluorine exchanges on trichloromethyl groups alpha to sulfur, oxygen and carbon atoms can be obtained.
- Saint-Jalmes, Laurent
-
-
- Synthesis, structure and reactivity of a trifluoromethyl sulfide anionic salt stabilized with tetrakis(dimethylamino)ethylene dication (TDAE2+)
-
A synthesis of the stable ionic trifluoromethanethiolate salts, TDAE2+2SCF3- (1) and TDAE2+SCF3-Cl- (2) was accomplished in quantitative yields via reduction of bis(trifluoromethyl) disulfide and trifluoromethanesulfenyl chloride using tetrakis(dimethylamino) ethylene (TDAE). The salts were found to be stable up to their melting points. The trifluoromethanethiolate salt [TDAE2+2SCF3- (1)] was for the first time characterized by X-ray structural analysis (orthorhombic, Pbca, a = 1434.0(1), b = 1178.1(1), c = 2203.2(1) pm) and cyclic voltammetry. Several reactions show the synthetic utility of this new reagent.
- Kolomeitsev, Alexander,Medebielle, Maurice,Kirsch, Peer,Lork, Enno,Roeschenthaler, Gerd-Volker
-
p. 2183 - 2185
(2007/10/03)
-
- Synthetic Uses of Thio- and Selenoesters of Trifluoromethylated Acids. 1. Preparation of Trifluoromethyl Sulfides and Selenides
-
Trifluorothioacetates (CF3CO-S-R, from (CF3CO)2O and thiols) as well as trifluoromethanethio-or trifluoromethaneselenosulfonates (CF3SO2-Y-R; Y = S, Se; from CF3SO2Na, RYYR, and Br2) can be formally decarbonylated or desulfonylated, respectively, provided that they are photolyzed at 40°C in the presence of 1 equiv of the corresponding disulfide or diselenide. Trifluoromethyl sulfides or selenides are obtained, and the added disulfide (or diselenide) is recovered after reaction. In such a way, S-(trifluoromethyl)cysteine derivatives can be obtained.
- Billard, Thierry,Roques, Nicolas,Langlois, Bernard R.
-
p. 3813 - 3820
(2007/10/03)
-
- Preparation of trifluoromethyl sulfides or selenides from trifluoromethyl trimethylsilane and thiocyanates or selenocyanates
-
Trifluoromethyl sulfides (or selenides) are easily obtained in one pot at 0°C from thiocyanates (or selenocyanates), commercial trifluoromethyl trimethylsilane and catalytic amounts of tetrabutylammonium fluoride (TBAF).
- Billard, Thierry,Large, Sylvie,Langlois, Bernard R.
-
-
- Process for the preparation of perhaloalkylthioethers
-
The present invention relates to a process for the preparation of perhaloalkylthioethers by bringing a perhaloalkyl halide, preferably a bromide or an iodide, into contact with a disulphide in the presence of zinc and of sulphur dioxide or of a dithionite or of a hydroxymethanesulphinate or of a formate anion and sulphur dioxide.
- -
-
-
- REACTIONS OF BROMOTRIFLUOROMETHANE AND RELATED HALIDES PART VII CONDENSATIONS WITH THIOCYANATES AND ISOCYANATES IN THE PRESENCE OF ZINC
-
Reaction of zinc and bromotriflouromethane, or perfluroalkyliodides, with thiocyanates and isocyanates gives respectively trifluromethylsulfides and substituted trifluroacetamides, as well as their long chain analogs.
- Tordeux, M.,Francese, C.,Wakselman, C.
-
-
- Tris(disubstituted amino)sulfonium perfluoroalkoxides and perfluoroalkylmercaptides and process for their preparation
-
Tris(disubstituted amino)sulfonium perfluoroalkoxides and tris(disubstituted amino)sulfonium perfluoroalkylmercaptides and process for their preparation.
- -
-
-
- Free-Radical Reactions of Fluoroalkanesulfenyl Halides. 4. Reactions of Perfluoroalkane- and Pentafluorobenzenesulfenyl Chlorides with Hydrocarbons in the Presence of Fluorinated Disulfides
-
Free-radical reactions of perfluoroalkanesulfenyl chlorides and pentafluorobenzenesulfenyl chloride with cyclohexane and toluene were carried out in the presence of bis(perfluoroalkyl) disulfides and bis(pentaflurophenyl)disulfide to assess the competition between the disulfide and the sulfenyl chloride for reaction with hydrocarbon radicals.With added bis(perfluoroalkyl) disulfides, radical attack occurs only on the sulfenyl chloride, but with added bis(pentafluorophenyl) disulfide, attack occurs on both sulfenyl chloride and disulfide.
- Harris, J. F.
-
p. 268 - 271
(2007/10/02)
-