1648-06-2

Upstream product

• 24925-18-6 phenyl(trifluoromethyl)mercury 
• 958-80-5 bis(4-methoxyphenyl)thione 
• 81290-20-2 (trifluoromethyl)trimethylsilane 
• 696-62-8 para-iodoanisole 
• 1256278-61-1 2,2-difluoro-1-tributylstannylethenyl p-toluenesulfonate 
• 1221-72-3 Bis(p-methoxyphenyl)diazomethan 
• 90-96-0 bis(p-methoxyphenyl)methanone 
• 5720-07-0 4-methoxyphenylboronic acid 
• 104-92-7 1-bromo-4-methoxy-benzene 

Relevant academic research and scientific papers

Fluoride-assisted trifluoromethylation of aromatic thiones with (trifluoromethyl)trimethylsilane

In the presence of a stoichiometric amount of Bu4NF·3H2O, (trifluoromethyl)trimethylsilane reacts with aromatic thiones in both thiophilic and carbophilic ways to deliver, in medium yield, a mixture of (trifluoromethylthio)diarylmethane and 1,1-diaryl-2,2,2-trifluoroethanethiol, the former product being the major one.

Studies on reactions of thioketones with trimethyl(trifluoromethyl)silane catalyzed by fluoride ions

Treatment of 2,2,4,4-tetramethylcyclobutane-1,3-dione (6) in THF with CF3SiMe3 in the presence of tetrabutylammonium fluoride (TBAF) yielded the corresponding 3-(trifluoromethyl)-3-[(trimethylsilyl)oxy]cyclobutanone 7 (Scheme 1) via nucleophilic addition of a CF3- anion at the C=O group and subsequent silylation of the alcoholate. Under similar conditions, the 'monothione' 1 reacted to give thietane derivative 8 (Scheme 2), whereas in the case of 'dithione' 2 only the dispirodithietane 9, the dimer of 2, was formed (Scheme 3). A conceivable mechanism for the formation of 8 is the ring opening of the primarily formed CF3 adduct A followed by ring closure via the S-atom (Scheme 2). In the case of thiobenzophenones 4, complex mixtures of products were obtained including diarylmethyl trifluoromethyl sulfide 10 and 1,1-diaryl-2,2-difluoroethene 11 (Scheme 4). Obviously, competing thiophilic and carbophilic addition of the CF3- anion took place. The reaction with 9H-fluorene-9-thione (5) yielded only 9,9′-bifluorenylidene (14; Scheme 6); this product was also formed when 5 was treated with TBAF alone. Treatment of 4a with TBAF in THF gave dibenzhydryl disulfide (15; Scheme 7), whereas, under similar conditions, 1 yielded the 3-oxopentanedithioate 17 (Scheme 9). The reaction of dithione 2 with TBAF led to the isomeric dithiolactone 16 (Scheme 8), and 3 was transformed into 1,2,4-trithiolane 18 (Scheme 10).

Aryl gem-Difluorovinyl Pinacolboronates: Synthesis and Utility for Suzuki-Miyaura Coupling Reaction

The synthesis of unstable aryl difluorovinyl pinacolboronates was achieved by the dehydrofluorination of α-trifluoromethyl arylmethyl pinacolboronates with LDA. These aryl difluorovinyl pinacolboronates can be used for Suzuki-Miyaura coupling with various

Cross-Coupling between Difluorocarbene and Carbene-Derived Intermediates Generated from Diazocompounds for the Synthesis of gem-Difluoroolefins

Cross-coupling between difluorocarbene and carbene-derived intermediates generated from diazocompounds was developed to give gem-difluoroolefins, which constitutes a fast practical pathway to achieve hindered gem-difluoroolefins. The cross-coupling between difluorocarbene and aryl diazoacetates proceeded smoothly in the presence of a copper source, whereas its coupling with diaryl diazomethanes occurred well under metal-free conditions. A mechanism involving a copper-difluorocarbene complex was proposed.

Consecutive cross-coupling reactions of 2,2-difluoro-1-iodoethenyl tosylate with boronic acids: Efficient synthesis of 1,1-diaryl-2,2-difluoroethenes

The cross-coupling reactions of 2,2-difluoro-1-iodoethenyl tosylate (2) with 2 equiv of boronic acids in the presence of catalytic amounts of Pd(OAc)2 and Na2CO3 afforded the mono-coupled products 3 and 5 in high yields. The use of 4 equiv of boronic acid

Preparation of (2,2-difluoroethenylidene)bis(tributylstannane) and arylation reaction: Efficient approach to 1,1-diaryl-2,2-difluoroethenes

Reaction of 2,2-difluoro-1-tributylstannylethenyl p-toluenesulfonate (1) with bis(tributyltin) in the presence of 5 mol % Pd(PPh3)4 and 30 equiv LiBr in THF at reflux temperature for 7 h afforded (2,2-difluoroethenylidene)bis(tributylstannane) (2) in a 70% yield. Coupling reaction of 2 with aryl iodides in the presence of 5 mol % Pd(PPh 3)4 and 5 mol % CuI in DMF at 80 °C for 3-4 h provided the coupled products 3 in 59-85% yields.

First synthesis of gem-difluorothiiranes from cycloaliphatic thioketones and difluorocarbene

The reaction of sterically crowded cycloaliphatic thioketones with phenyl(trifluoromethyl)mercury and sodium iodide in boiling benzene yielded gem-difluorothiiranes in fair yields whereas in the case of aromatic thioketones gem-difluoroalkenes were obtain