90784-42-2

Upstream product

• 82477-48-3 diethyl α-bromodifluoromethyl-α-phenylmalonate 
• 129946-88-9 Umemoto's reagent 
• 101-97-3 Ethyl 2-phenylethanoate 
• 1117-96-0 Diazoethan 
• 56539-85-6 α-(trifluoromethyl)-phenylacetic acid 
• 1979-51-7 1,1,3,3,3-pentafluoro-2-phenylpropene 
• 141-52-6 sodium ethanolate 
• 2314-97-8 iodotrifluoromethane 
• 31491-20-0 (1-ethoxy-2-phenylvinyloxy)trimethylsilane 
• 22065-57-2 ethyl 2-phenyldiazoacetate 
• 85278-32-6 ethyl 2-phenyl-3,3-difluoroacrylate 
• 536-74-3 phenylacetylene 
• 887144-94-7 Togni's reagent II 
• 78935-61-2 (Z)-((1-ethoxy-2-phenylvinyl)oxy)trimethylsilane 

Downstream Products

• 113242-93-6 2-Phenyl-2-trifluormethyl-ethanol 
• 56539-85-6 α-(trifluoromethyl)-phenylacetic acid 

Relevant academic research and scientific papers

Stereoselective Synthesis of Difluorinated 1,3-Dienes via Palladium-Catalyzed C-F Bond Activation of Tetrasubstituted gem-Difluoroalkenes

A highly diastereoselective Pd(0)-catalyzed synthesis of difluorinated 1,3-dienes is described. Symmetrical 1,3-dienes containing a vicinal difluoro moiety can be obtained as single diastereomers from tetrasubstituted gem-difluoroalkenes. The reaction presumably proceeds through a stereoselective twofold Pd-catalyzed Miyaura borylation/Suzuki-Miyaura cross-coupling of the C-F bond. Moreover, modular synthesis of unsymmetrical difluorinated 1,3-dienes is also achievable by the coupling between gem-difluoroalkenes and borylated monofluoroalkenes.

Palladium-Catalyzed Stereoselective Hydrodefluorination of Tetrasubstituted gem-Difluoroalkenes

A highly stereoselective palladium(0)-catalyzed hydrodefluorination (HDF) of tetrasubstituted gem-difluoroalkenes is developed. By using catalytic Pd(PPh3)4 (2.5-5 mol percent) and hydrosilane Me2PhSiH, various trisubstituted terminal (E)-monofluoroalkenes can be synthesized with excellent E/Z selectivity (>99:1) and good functional group tolerability. The key stereocontrol should be exerted by an ester-directed C-F bond oxidative addition step in the catalytic cycle.

Stereoselective Palladium-Catalyzed C?F Bond Alkynylation of Tetrasubstituted gem-Difluoroalkenes

A stereoselective Pd(PPh3)4-catalyzed C?F bond alkynylation of tetrasubstituted gem-difluoroalkenes with terminal alkynes has been developed. This method gives access to a great variety of conjugated monofluoroenynes bearing a tetrasubstituted alkene moiety with well-defined stereochemistry. Chelation-assisted oxidative addition of Pd to the C?F bond is proposed to account for the high level of stereocontrol. An X-ray crystal structure of a key monofluorovinyl PdII intermediate has been obtained for the first time as evidence for the proposed mechanism.

Organosilicon Reducing Reagents for Stereoselective Formations of Silyl Enol Ethers from α-Halo Carbonyl Compounds

Salt-free stereoselective synthesis of silyl enol ethers was achieved by treating α-halo carbonyl compounds with 2,3,5,6-tetramethyl-1,4-bis(trimethylsilyl)-1,4-dihydropyrazine. In this reaction, easily removable trimethylsilyl halides and 2,3,5,6-tetramethylpyrazine were generated as the reaction byproducts. Due to the inertness of the reaction byproducts, we found a one-pot transformation of the in situ generated silyl enol ethers into various α-functionalized carbonyls by reaction with Togni-II reagent or aldehydes.

Cu-Mediated Trifluoromethylation of Aromatic α-Diazo Esters with the Yagupolskii–Umemoto Reagent

Reductive trifluoromethylation of aromatic α-diazo esters at room temperature with the Yagupolskii–Umemoto reagent {[Ph2SCF3][OTf]; (2a)} in DMF in the presence of excess CuCl gave a variety of α-trifluoromethyl arylacetates in up to

Copper-Mediated Deuterotrifluoromethylation of α?Diazo Esters

A copper-mediated deuterotrifluoromethylation of α?diazo esters under the promotion of deuterium oxide (D2O) has been developed for the synthesis of deuterium-labeled trifluoromethyl compounds. This deuterotrifluoromethylation reaction is of broad scope and can afford the deuterated products with higher than 99% isotopic purity. Moreover, the results of this investigation also provide some experimental evidences to support our previously proposed trifluoromethylation mechanism.

Copper-mediated trifluoromethylation of α-diazo esters with TMSCF3: The important role of water as a promoter

Copper-mediated trifluoromethylation of α-diazo esters with TMSCF3 reagent has been developed as a new method to prepare α-trifluoromethyl esters. This trifluoromethylation reaction represents the first example of fluoroalkylation of a non-fluorinated carbene precursor. Water plays an important role in promoting the reaction by activating the "CuCF3" species prepared from CuI/TMSCF3/CsF (1.0:1.1:1.1). The scope of this trifluoromethylation reaction is broad, and its efficiency is demonstrated in the synthesis of a variety of aryl-, benzyl-, and alkyl-substituted 3,3,3-trifluoropropanoates.

Exclusive aromatic vs aliphatic C-H bond functionalization by carbene insertion with gold-based catalysts

The direct functionalization of aromatic C-H bonds by carbene insertion from diazo compounds catalyzed by gold complexes with N-heterocyclic ligands is described. The reaction is completely selective toward the C sp2-H bonds, other C sp3-H bonds remaining unreacted. A study with several NHC ligands in Au(I) and Au(III) complexes has been performed. The potential application of this strategy to give profen derivatives has also been explored.

Mechanistic studies on α-trifluoromethylation of ketones via silyl enol ethers and its application to other carbonyl compounds

(Chemical Equation Presented) Synthesis of α-CF3 carbonyl compounds has been recognized to be difficult up to now because the polarization of CF3δ--Iδ+ is opposite to that of CH3δ+-Iδ-, and this makes it difficult to introduce CF3+ unit to enolates. We recently reported an effective R-trifluoromethylation of ketones by using Et 2Zn with Rh catalyst, but the mechanism has not fully been cleared. Now, we carried out the detailed mechanistic studies and found the involvement of a highly reactive alkylrhodium complex which derived from Et2Zn and RhCl(PPh3)3 in this α-trifluoromethylation. Furthermore, this α-trifluoromethylation was applied to other types of carbonyl compounds in good yields.

Efficient one step procedure for the synthesis of α- trifluoromethylated arylacetates

The reaction of β,β-difluoro-α-trifluoromethylstyrene derivatives 1 with 3 equiv. of sodium methoxide in acetonitrile at 25°C afforded a- trifluoromethylated arylacetates 3 in good yields.