56210-75-4

Upstream product

• 867-13-0 diethoxyphosphoryl-acetic acid ethyl ester 
• 434-45-7 2,2,2-Trifluoroacetophenone 
• 83961-56-2 4,4,4-trifluoro-3-oxo-2-(triphenylphosphoranylidene)butanoic acid ethyl ester 
• 591-51-5 phenyllithium 
• 1099-45-2 ethyl (triphenylphosphoranylidene)acetate 
• 108-86-1 bromobenzene 
• 25597-16-4 ethyl 4,4,4-trifluorocrotonate 
• 153816-93-4 Ethyl 3-hydroxy-3-phenyl-4,4,4-trifluorobutyrate 
• 81290-20-2 (trifluoromethyl)trimethylsilane 
• 152876-60-3 ethyl (2Z)-3-iodo-3-phenylprop-2-enoate 
• 623-73-4 diazoacetic acid ethyl ester 

Downstream Products

• 2143-93-3 (Z)-3-phenyl-4,4,4-trifluoro-2-butenoic acid 
• 648425-37-0 (2Z)-3-trifluoromethyl-3-phenylprop-2-en-1-ol 
• 56210-74-3 ethyl (2E)-3-trifluoromethyl-3-phenylprop-2-enoate 
• 648425-30-3 (2Z)-3-trifluoromethyl-3-phenylprop-2-en-1-yl chloride 

Relevant academic research and scientific papers

Copper-Photocatalyzed Contra-Thermodynamic Isomerization of Polarized Alkenes

The contra-thermodynamic isomerization of α- and β-substituted cinnamate derivatives catalyzed by the Cu(OAc)2/rac-BINAP complex under blue light irradiation is reported. The use of an oxazolidinone template, which favored the complexation of the copper catalyst to the substrate, allowed the E → Z isomerization of the catalytically formed chromophore under simple and robust reaction conditions in good to excellent ratios. The mechanism of this process based on the transient formation of a chromophore was also studied.

Spatiotemporal Control of Pre-existing Alkene Geometry: A Bio-Inspired Route to 4-Trifluoromethyl-2H-chromenes

Routes to prepare C4-trifluoromethyl analogues of the 2H-chromene scaffold are scarce: this is particularly striking given the importance of fluorine in pharmaceutical development. To address this limitation, a facile strategy has been developed that is reliant on catalytic, geometric isomerization of easily accessible allylic alcohols (up to >95:5) followed by intramolecular cyclization via Pd catalysis (up to 96%). This concise biomimetic approach emulates the photoisomerization/cyclization cascade inherent to phenylpropanoid biosynthesis.

A Bio-Inspired, Catalytic e → Z Isomerization of Activated Olefins

Herein, Natures flavin-mediated activation of complex (poly)enes has been translated to a small molecule paradigm culminating in a highly (Z)-selective, catalytic isomerization of activated olefins using (-)-riboflavin (up to 99:1 Z/E). In contrast to the prominent Z → E isomerization of the natural system, it was possible to invert the directionality of the isomerization (E → Z) by simultaneously truncating the retinal scaffold, and introducing a third olefin substituent to augment A1,3-strain upon isomerization. Consequently, conjugation is reduced in the product chromophore leading to a substrate/product combination with discrete photophysical signatures. The operationally simple isomerization protocol has been applied to a variety of enone-derived substrates and showcased in the preparation of the medically relevant 4-substituted coumarin scaffold. A correlation of sensitizer triplet energy (ET) and reaction efficiency, together with the study of additive effects and mechanistic probes, is consistent with a triplet energy transfer mechanism.

Synthesis of β-CF3 ketones from trifluoromethylated allylic alcohols by ruthenium catalyzed isomerization

This work describes the optimization process for the synthesis of β-trifluoromethylated ketones from trifluoromethylated allylic alcohols. This transformation proceeds through a ruthenium catalyzed isomerization under mild conditions with high atom econom

Wittig reaction with ion-supported Ph3P

Ion-supported Ph3P, 4-(diphenylphosphino)benzyltrimethylammonium bromide A and N-methyl-N-[4-(diphenylphosphino)benzyl]pyrrolidinium bromide B, were used for the Wittig reaction. Ion-supported phosphonium salts A1 and B1, which were prepared from the reactions of ion-supported Ph3P A and B with ethyl bromoacetate, respectively, reacted with aromatic and aliphatic aldehydes in the presence of K2CO3 to give the corresponding α,β-unsaturated ethyl esters in good yields with high purity by simple filtration of the reaction mixture and subsequent removal of the solvent from the filtrate. Similarly, ion-supported phosphonium salts A2 and B2, which were prepared from the reactions of ion-supported Ph3P A and B with p-methylbenzyl bromide, respectively, reacted with aromatic and aliphatic aldehydes in the presence of NaH to provide the corresponding p-methylstyrene derivatives in good yields with high purity by simple filtration of the reaction mixture and the subsequent removal of the solvent from the filtrate. In both reactions, the co-product, ion-supported Ph3PO, could be obtained quantitatively by simple filtration, and was converted into the corresponding ion-supported Ph3P A and B again in high yields using dimethyl sulfate, followed by the reduction with LiAlH4. Recovered and regenerated ion-supported Ph3P A and B could be reused for the same Wittig reaction while maintaining good yields of ethyl (E)-3-(4′-chlorophenyl)-2-propenoate and 1-(4′-chlorophenyl)-2- (4″-methylphenyl)ethene with high purity by simple filtration and removal of the solvent from the filtrate.

Olefination reactions using tetraarylphosphonium (TAP)-supported phosphorus ylides

Tetraarylphosphonium (TAP)-supported phosphorus ylides were prepared and used in copper-catalyzed olefination reactions with diazo compounds to produce conjugated esters, amides, and phosphonates. The TAP-phosphine oxide can easily be separated from the alkene product, recycled, and reused. Georg Thieme Verlag Stuttgart ? New York.

Efficient trifluoromethylation of activated and non-activated alkenyl halides by using (trifluoromethyl)trimethylsilane

An efficient method for the trifluoromethylation of halogenated double bonds by using in situ generated "trifluoromethyl copper" is described. Herein, the most common trifluoromethyl source, (trifluoromethyl) trimethylsilane, was converted selectively int

Construction of optically active CF3-containing quaternary carbon centers via stereospecific SN2′ reaction

(Chemical Equation Presented) Phosphates from 3-substituted 4,4,4-trifluorobut-2-en-1-ols were found to be effective for construction of CF3-containing quaternary carbon centers by way of Cu(I)-catalyzed Grignard reactions in the presence of ca

Efficient and stereoselective synthesis of β-trifluoromethyl α,β-unsaturated esters via iron(III) porphyrin-catalyzed olefination of ketones

β-Trifluoromethyl α,β-unsaturated esters were efficiently prepared by reactions of fluorine-containing ketones with diazo compounds via metalloporphyrin-catalyzed olefination in the presence of triphenylphosphine. The commercially available Fe(III)(TPP)Cl (TPP: tetraphenylporphyrin) is effective for catalyzing the olefination of a variety of trifluoromethyl ketones with different diazoacetate esters under mild conditions. The reactions proceeded with high yields (up to 95% isolated yield) and high stereoselectivity (up to 99% (E)-selectivity).

Synthesis of novel diazatricyclodecanes (DTDs). Effects of structural variation at the C3′ allyl end and at the phenyl ring of the cinnamyl chain on μ-receptor affinity and opioid antinociception

Two series of analogues of 9-propionyl-10-cinnamyl-9,10-diazatricyclo[4.2.1.12,5]decane (1a) and 2-propionyl-7-cinnamyl-2,7-diazatricyclo[4.4.0.03,8]decane (2a), in which the cinnamyl moiety was replaced by various aralkenyl chains,