130654-80-7

Upstream product

• 529-28-2 4-iodoanisol 
• 672339-38-7 (Z)-2,3,3,3-tetrafluoro-1-iodoprop-1-ene 
• 887144-97-0 Togni's reagent 
• 767-91-9 1-ethynyl-2-methoxybenzene 
• 615-41-8 2-iodochlorobenzene 
• 105273-33-4 1-chloro-2-(trimethylsilylethynyl)benzene 
• 7342-00-9 3-(2-methoxyphenyl)prop-2-ynoic acid 
• 81290-20-2 (trifluoromethyl)trimethylsilane 
• 40230-91-9 [(2-methoxyphenyl)ethynyl]trimethylsilane 
• 77152-08-0 trifluoromethylcopper(I) 
• 1514-82-5 2-bromo-3,3,3-trifluoropropene 
• 661-54-1 3,3,3-trifluoroprop-1-yne 

Downstream Products

• 130654-91-0 3,3,3-trifluoro-1-(2-methoxyphenyl)propan-1-one 
• 130654-92-1 o-(3,3,3-trifluoro-1-iodo-1-propenyl)anisole 
• 1309369-62-7 C₁₇H₁₃F₃O₃ 
• 1567353-96-1 (Z)-3,3,3-trifluoro-1-(2-methoxyphenyl)-1-tributylstannyl-2-trimethylsilyl-1-propene 
• 1567354-02-2 (Z)-3,3,3-trifluoro-1-(2-methoxyphenyl)-2-tributylstannyl-1-trimethylsilyl-1-propene 

Relevant academic research and scientific papers

Regioselective Gold-Catalyzed Hydration of CF3- and SF5-alkynes

The regioselective gold-catalyzed hydration of CF3- and SF5-alkynes is described. The corresponding trifluoromethylated and pentasulfanylated ketones are obtained in up to 91% yield as single regioisomers showcasing the use of CF3 and SF5 as highly efficient directing groups in this reaction. Notably, this transformation represents the first use of CF3- and SF5-alkynes in gold catalysis.

Dual-gold(I)-generated trifluoromethylation of terminal alkynes with Togni's reagent

The interaction of a Au(I) catalyst (JohnPhosAu(I)-MeCN/SbF6) and the Togni's reagent 1, as a source of electrophilic trifluoromethyl group, has been studied in order to develop gold-catalysed alkyne trifluoromethylation reactions. Alkyne-CF3products were prepared in moderate yields (up to 46%) by electrophilic trifluoromethylation of terminal arylalkynes with Togni's reagent 1 in the presence of sub-stoichiometric amounts of gold catalyst (25%). The proposed addition-elimination reaction mechanism proceeds through a Au-Togni Reagent complex with a linear Togni Reagent-O-Au(I)-P-(phosphane) coordination mode (X-ray analysis). Alkyne deprotonation gives rapid formation of protonated Togni Reagent and a σ,π-acetylide dual-Au complex, confirmed by X-ray analysis. It was shown that the σ,π-dual-Au complex activates for trifluoromethylation, most likely by transfer of a [LAu]+fragment to the alkyne substrate. The resulting reactive π-Au+-alkyne intermediate probably undergoes O-/CF3-addition of Togni Reagent, and final elimination of Togni alcohol gives the alkyne-CF3product.

Fluoroform-Derived CuCF3 for Trifluoromethylation of Terminal and TMS-Protected Alkynes

An efficient trifluoromethylation reaction of alkynes using a fluoroform-derived CuCF3 reagent is described. The CF3 source is the inexpensive industrial waste fluoroform (CF3H). The air-stable CuCF3 reagent can be prepared in large quantities and is convenient to use. Synthetically useful trifluoromethylated alkynes containing a wide range of functional groups were successfully synthesized under mild conditions. Both terminal and TMS-protected alkynes gave the products in one step. The beneficial effect of a diamine ligand tetramethylethylenediamine (TMEDA) with the fluoroform-derived CuCF3 reagent was also demonstrated.

Cu(I)/Ag(I)-mediated decarboxylative trifluoromethylation of arylpropiolic acids with Me3SiCF3at room temperature

A novel Cu(I)/Ag(I)-mediated decarboxylative trifluoromethylation of arylpropiolic acids with Me3SiCF3has been developed for the construction of Csp-CF3bond under mild conditions. This method proceeds smoothly at room temperature and shows a widely functional compatibility, providing a series of corresponding trifluoromethylated acetylenyl-containing aromatics in good yields.

Practical methods for the synthesis of trifluoromethylated alkynes: Oxidative trifluoromethylation of copper acetylides and alkynes

Two practical and complementary methods are reported for the synthesis of trifluoromethylated alkynes. The first one, a mix-and-stir process, is based on the oxidative trifluoromethylation of readily available and bench-stable copper acetylides while the second one, which displays a broad substrate scope and has several advantages over existing procedures, is based on the oxidative copper-catalyzed direct trifluoromethylation of terminal alkynes. Both reactions provide user-friendly processes for the synthesis of trifluoromethylated acetylenes which can be easily obtained from readily available starting materials.

Facile syntheses of various per- or polyfluoroalkylated internal acetylene derivatives

Treatment of per- or polyfluoroalkylated vinyl iodides 5 with 2equiv. of n-BuLi in THF produced the corresponding lithium acetylides in situ, which were transformed into zinc acetylides by the addition of ZnCl2· TMEDA complex into the reaction mixture. The in situ generated zinc acetylides were exposed to the cross-coupling conditions such as ArI/cat. Pd(PPh 3)4, reflux, 6-12 h, giving rise to the desired per- or polyfluoroalkylated acetylenes in high yields. In the case of trifluoromethylated acetylene, commercially available 2-bromo-3,3,3-trifluoropropene 6 could also be used instead of 5 as the starting material. In the acetylenes having a fluoroalkyl group and an aliphatic side chain, vinyl iodides 7, prepared by radical addition of perfluoroalkyl iodide to terminal acetylenes, were treated with t-BuOK at room temperature or at the reflux temperature of benzene, affording the desired compounds in good yields.

Preparation of 1-Aryl- or 1-Alkenyl-2-(perfluoroalkyl)acetylenes

1-Aryl- or 1-alkenyl-2-(perfluoroalkyl)acetylenes were produced in high yields by coupling reaction of aryl or alkenyl iodides with (perfluoroalkynyl)zinc compounds prepared from the corresponding (perfluoroalkyl)acetylenes in the presence of Pd catalyst.