- Borazine-CF3? Adducts for Rapid, Room Temperature, and Broad Scope Trifluoromethylation
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A fluoroform-derived borazine CF3? transfer reagent is used to effect rapid nucleophilic reactions in the absence of additives, within minutes at 25 °C. Inorganic electrophiles spanning seven groups of the periodic table can be trifluoromethylated in high yield, including transition metals used for catalytic trifluoromethylation. Organic electrophiles included (hetero)arenes, enabling C?H and C?X trifluoromethylation reactions. Mechanistic analysis supports a dissociative mechanism for CF3? transfer, and cation modification afforded a reagent with enhanced stability.
- Geri, Jacob B.,Wade Wolfe, Michael M.,Szymczak, Nathaniel K.
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supporting information
p. 1381 - 1385
(2018/01/15)
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- COMPLEXES FOR NUCLEOPHILIC, RADICAL, AND ELECTROPHILIC POLYFLUOROALKYLATION
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Disclosed herein are borazine complexes and use of the same in perfluoroalkylation reactions.
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Paragraph 00135
(2018/04/11)
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- Electrophilic Trifluoromethyl- and Fluoroalkylselenolation of Organometallic Reagents
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Fluoroalkylseleno groups are emerging groups that still suffer from a lack of efficient methods for introduction onto organic molecules. Herein, we describe an efficient method to perform reactions between in situ formed fluoroalkaneselenyl chlorides and organometallic reagents. With this strategy, various fluoroalkylselenolated molecules were easily obtained. Furthermore, the Hansch parameter of the CF3Se group was determined for the first time.
- Glenadel, Quentin,Ismalaj, Ermal,Billard, Thierry
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supporting information
p. 530 - 533
(2017/02/05)
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- Silver-catalyzed fluoroalkylation of thiols using fluoroalkanesulfinates
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A practical sliver-catalyzed fluoroalkylation of aryl-, heteroaryl- and alkylthiols has been developed. The reaction has a good functional-group tolerance and excellent selectivity. A variety of stable and solid fluoroalkanesulfinates including di- and perfluoroalkanesulfinates can be employed. This methodology provides a straightforward and streamlined access to perfluoroalkylthiolated organic molecules. [Figure presented]
- Ma, Jing-jing,Liu, Qi-ran,Lu, Guo-ping,Yi, Wen-bin
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supporting information
p. 113 - 117
(2017/01/03)
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- S-Trifluoromethylation of Thiols by Hypervalent Iodine Reagents: A Joint Experimental and Computational Study
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The radical trifluoromethylation of thiophenol in condensed phase applying reagent 1 (3,3-dimethyl-1-(trifluoromethyl)-1λ3,2-benziodoxol) has been examined by both theoretical and experimental methodologies. On the basis of ab initio molecular
- Sala, Oliver,Santschi, Nico,Jungen, Stefan,Lüthi, Hans Peter,Iannuzzi, Marcella,Hauser, Nicole,Togni, Antonio
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supporting information
p. 1704 - 1713
(2016/02/20)
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- Trifluoromethylation of thiophenols and thiols with sodium trifluoromethanesulfinate and iodine pentoxide
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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
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p. 417 - 421
(2016/02/03)
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- General synthesis of trifluoromethyl selenides utilizing selenocyanates and fluoroform
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Trifluoromethylated selenoethers are quite rare despite their potential and the interest that they generate. A series of trifluoromethylseleno derivatives, either primary and secondary aliphatic or aromatic and heterocyclic, is described herein by the reaction of easily prepared organic selenocyanates and CuCF3. Another beneficial feature of this reaction is the use of fluoroform as a source for the CF3 group, a compound whose chemistry is currently being intensively researched because it is a potent greenhouse gas that should not be released into the atmosphere.
- Potash, Shay,Rozen, Shlomo
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p. 11205 - 11208
(2015/02/19)
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- Alkoxide-induced nucleophilic trifluoromethylation using diethyl trifluoromethylphosphonate
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A novel alkoxide-induced nucleophilic trifluoromethylation of carbonyl compounds, disulfides, and diselenides using diethyl trifluoromethylphosphonate is presented. In these reactions diethyl trifluoromethylphosphonate acts as a [CF3-] synthon.
- Cherkupally, Prabhakar,Beier, Petr
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experimental part
p. 252 - 255
(2010/03/24)
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- Nucleophilic perfluoroalkylation of aldehydes, ketones, imines, disulfides, and diselenides
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Using a procedure analogous to that developed for nucleophilic trifluoromethylation, the perfluoroalkyl anion reagents created by mixing C 2F5I and n-C4F9I with tetrakis(dimethylamino)ethylene (TDAE) were effective in their nucleophilic reactions with aldehydes, ketones, imines, disulfides, and diselenides. Irradiation proved beneficial in the aldehyde and ketone reactions.
- Pooput, Chaya,Dolbier Jr., William R.,Medebielle, Maurice
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p. 3564 - 3568
(2007/10/03)
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- A New and Efficient Method for the Synthesis of Trifluoromethylthio- and Selenoethers
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(Equation presented) A new atom-economic procedure for preparation of trifluoromethyl thio- and selenoethers is reported, wherein both halves of aryl and alkyl disulfides and diselenides are able to be utilized with high efficiency.
- Pooput, Chaya,Medebielle, Maurice,Dolbier Jr., William R.
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p. 301 - 303
(2007/10/03)
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- New stable reagents for the nucleophilic trifluoromethylation. Part 4: Trifluoromethylation of disulfides and diselenides with hemiaminals of trifluoroacetaldehyde
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Hemiaminals of fluoral and derivatives have been previously described as efficient new reagents for the nucleophilic trifluoromethylation of carbonyl compounds. Their use has been extended to the synthesis of trifluoromethyl sulfides and selenides from di
- Blond, G.,Billard, T.,Langlois
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p. 2473 - 2475
(2007/10/03)
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- A convenient access to perfluoroalkyl selenoethers selenyl chlorides
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The treatment of diselenides with different perfluoroalkyl iodides in the presence of sodium hydroxymethanesulfinate led to perfluoroalkyl selenides in fair to good yields. The reaction between benzyl perfluorooctyl selenide chlorine, or sulfuryl chloride
- Magnier,Vit,Wakselman
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p. 1260 - 1262
(2007/10/03)
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- Nucleophilic trifluoromethylation of carbonyl compounds and disulfides with trifluoromethane and silicon-containing bases
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Provided that DMF (or another N,N-dialkylformamide) is present in the reaction medium, at least in a catalytic amount, fluoroform trifluoromethylates efficiently carbonyl compounds, even enolizable ones, when opposed to (TMS)2N- M+, generated in situ from N(TMS)3 and M+ F- or RO- Na+. When F- is used in a catalytic amount, silylated α-(trifluoromethyl)carbinols are obtained: In this case, the four-component system HCF3/N(TMS)3/catalytic F-/catalytic DMF behaves like the Ruppert's reagent, especially as far as nonenolizable carbonyl compounds are concerned (CF3SiMe3 remains more efficient for enolizable carbonyl compounds). This process involves an adduct between DMF and -CF3 which is the true trifluoromethylating agent. In the same way, fluoroform efficiently trifluoromethylates disulfides and diselenides when deprotonated with a strong base selected from t-BuOK or N(SiMe3)3/Me4NF (or TBAT). t-BuOK is more adapted to the trifluoromethylation of awl disulfides whereas N(SiMe3)3/F- is Well suited to that of aliphatic disulfides.
- Large,Roques,Langlois
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p. 8848 - 8856
(2007/10/03)
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- Synthetic Uses of Thio- and Selenoesters of Trifluoromethylated Acids. 1. Preparation of Trifluoromethyl Sulfides and Selenides
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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.
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p. 3813 - 3820
(2007/10/03)
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- Synthesis of Trifluoromethyl Selenides
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Alkyl and aryl trifluoromethylselenides are easily obtained from trifluoromethyl trimethylsilane and diselenides or selenocyanates as well as from sodium trifluoromethanesulfinate and diselenides or selenenyl chlorides, via trifluoromethaneselenosulfonate
- Billard, Thierry,Langlois, Bernard R.,Large, Sylvie
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p. 521 - 524
(2007/10/03)
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- Preparation of trifluoromethyl sulfides or selenides from trifluoromethyl trimethylsilane and thiocyanates or selenocyanates
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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.
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- A new simple access to trifluoromethyl thioethers or selenoethers from trifluoromethyl trimethylsilane and disulfides or diselenides
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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.
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p. 6865 - 6868
(2007/10/03)
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- PERFLUOROALKYL-SELENATION OF OLEFINS
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Perfluoroalkyl-selenation of olefins has been performed by the reaction of diphenyl diselenide with sodium borohydride followed with perfluoroalkyl halides (RfX) and olefins where one electron transfer from phenylseleno anion to RfX occurs, generating per
- Uneyama, Kenji,Kitagawa, Kouichi
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p. 375 - 378
(2007/10/02)
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