17659-27-7

Upstream product

• 93-99-2 benzoic acid phenyl ester 
• 340-04-5 1-phenyl-2,2,2-trifluoromethylethanol 
• 65-85-0 benzoic acid 
• 185424-21-9 Methanesulfonic acid 2,2,2-trifluoro-1-phenyl-ethyl ester 
• 884-09-3 phenyl thiobenzoate 
• 98-88-4 benzoyl chloride 
• 434-45-7 2,2,2-Trifluoroacetophenone 
• 66-99-9 β-naphthaldehyde 
• 49543-63-7 4-tert-butylbenzyl mercaptan 
• 100-52-7 benzaldehyde 
• 108-98-5 thiophenol 
• 17659-27-7 1-benzoyloxy-1-phenyl-2,2,2-trifluoroethane 
• 93-97-0 benzoic acid anhydride 
• 13652-07-8 phenyltrifluorodiazoethane 

Downstream Products

• 340-06-7 S(+)-1-phenyl-2,2,2-trifluoroethanol 

Relevant academic research and scientific papers

Functional group transformation of α-trifluoromethylated alcohol derivatives

Functional group transformation of α-trifluoromethylated alcohols was investigated. Nucleophilic substitutions of their sulfonates was achieved in the presence of metal fluoride as a base with complete inversion of the configuration.

Tropylium-Catalyzed O-H Insertion Reactions of Diazoalkanes with Carboxylic Acids

Herein, we describe the application of a nonbenzenoid aromatic carbocation, namely tropylium, as an organic Lewis acid catalyst in O-H functionalization reactions of diazoalkanes with benzoic acids. The newly developed protocol is applicable to a wide range of diazoalkane and carboxylic acid substrates with excellent efficiency (43 examples, up to 99% yield).

Synthesis, characterization and catalytic performances of benzimidazolin-2-iminato actinide (IV) complexes in the Tishchenko reactions for symmetrical and unsymmetrical esters

A new family of benzimdazolin-2-iminato actinide?(IV) complexes [(Bim7-MeDipp/MeN)An(N(SiMe3)2)3] (An = U (3), Th (4)) and [(Bim4-MeDipp/MeN)An(N(SiMe3)2)3] (An = U (5), Th (6)) were synthesized and their solid state structures were established by single-crystal X-ray diffraction analysis. The catalytic performances of complexes 3–6 towards the homo- and cross-coupling of aldehydes (Tishchenko reaction) were studied and the thorium complexes 4 and 6 displayed moderate to high activities for the production of the corresponding symmetric and unsymmetrical esters. Coupling of aldehyde and alcohols, known as the tandem proton-transfer esterification, and the intermolecular coupling reaction between aldehyde and trifluoromethylketones were also investigated by these thorium complexes, indicating a complementary method to obtain unsymmetrical esters selectively. Plausible mechanisms for these reactions are proposed based on stoichiometric studies.

Selenide ions as catalysts for homo- and crossed-Tishchenko reactions of expanded scope

Selenide ions have been shown to catalyze the Tishchenko reaction for the first time. These catalysts are superior to previously reported thiolate analogues and promote the disproportionation of aldehydes with increased reaction rates and broader scope at lower catalyst loadings and temperatures. Significantly improved catalyst performance was also observed in the aryl selenide mediated crossed intermolecular Tishchenko reaction.

Microwave-assisted efficient thiolate-catalysed homo- and crossed intermolecular Tishchenko reactions

Recently, the first efficient intermolecular crossed Tishchenko reactions were reported. The utility of these processes is curtailed by long reaction times of up to 4 days (at reflux). Herein we report that these reactions are highly susceptible to acceleration by microwave irradiation-allowing fast, efficient, high-yielding coupling to proceed in 10-180 min.

Tunable bromomagnesium thiolate tishchenko reaction catalysts: Intermolecular aldehyde-trifluoromethylketone coupling

(Figure Presented) Applied knowledge: A new thiolate-catalyzed Tishchenko reaction inspired by biochemical processes features exceptionally good control over the catalyst's steric/electronic properties. The isolation of reaction intermediates provided valua-ble insights into the reaction mechanism, which in turn has allowed the development of the first cross-Tishchenko coupling reactions between aldehydes and activated ketones (see example).

Nonenzymatic kinetic resolution of racemic 2,2,2-trifluoro-1-aryl ethanol via enantioselective acylation

Kinetic resolution of a series of 2,2,2-trifluoro-1-aryl ethanol with (R)-benzotetramisole as the catalyst has been investigated. The result showed that when the aryl group in the substrate was a phenyl (or a phenyl substituted by an electron-donating group) or a naphthyl (an extended phenyl) group, the system could give an s value higher than 20. Preparative KR examples demonstrated the applicability of this method in the preparation of some of enantiomerically pure 2,2,2-trifluoro-1-aryl ethanol or 2,2,2-trifluoro-1-aryl-ethyl iso-butyrate.

The effect of catechin derivatives on the enantioselectivity of lipase-catalyzed hydrolyses of alkynol benzoate esters

Polyphenols, such as (+)-catechin and pyrogallol could be used to enhance stereochemical control in the lipase-catalyzed hydrolysis of alkynol benzoate esters, leading to increased enantioselectivities in the kinetic resolution of alkynols with lipase Amano AH.

Alkylnickel and -palladium alkoxides associated with alcohols through hydrogen bonding

trans-PdR2L2(R = CH3, C2H5; L = PMe3, PEt3) and trans-NiMe2(PMe3)2 react with 2 equiv of fluorinated alcohols and para-substituted phenols to give complexes formulated as trans-PdR(OR′)(HOR′)L2 (R′ = CH(CF3)Ph, C6H5, p-CH3C6H4, p-CH3OC6H4, p-ClC6H4, P-BrC6H4, p-FC6H4) and trans-NiMe(OR′)(HOR′)(PMe3)2 (R′ = CH(CF3)Ph, C6H5), respectively. IR and NMR spectra of these complexes indicate the presence of strong O-H?O hydrogen bonding between the alkoxide (or aryloxide) ligand and the alcohol (or substituted and nonsubstituted phenol) both in the solid state and in solution. X-ray crystallography of trans-PdMe(OPh)(HOPh)(PMe3)2 and trans-NiMe(OPh)(HOPh)(PMe3)2 shows that the phenoxide oxygen in each complex is associated with phenol through hydrogen bonding. Reactions of trans-PdMe2(PMe3)2 with equimolar substituted and nonsubstituted phenols, respectively, give trans-PdMe(OC6H4-p-X)(PMe3)2 (X = H, Me, OMe, F, Cl, Br), which react with additional equimolar phenols to give phenol-bonded palladium complexes trans-PdMe(OC6H4-p-X)(HOC6H 4-p-X)(PMe3)2. trans-PdMe(OPh)(PMe3)2 reacts also with fluorinated alcohols to give trans-PdMe(OPh)(HOCH(CF3)Ph)(PMe3)2 and trans-PdMe(OPh)(HOCH(CF3)2)(PMe3)2, which are fully characterized by means of IR and NMR spectroscopy and X-ray crystallography. 1H NMR spectra of mixtures of phenol with cis-PdMe2(dmpe) (dmpe = 1,2-bis(dimethylphosphino)ethane) and cis-PdMe2(dpe) (dpe = 1,2-bis(diphenylphosphino)ethane) indicate formation of strong O-H?O hydrogen bonding between phenol and the phenoxide ligand in solution. Equilibrium constants for the association of phenol with the palladium phenoxide having dmpe ligand, obtained by means of 1H NMR spectroscopy, are smaller than those of trans-PdMe(OPh)(PMe3)2 with phenol. NMR spectra of trans-PdMe(OCH(CF3)Ph)(HOCH(CF3)Ph)(PMe3) 2 and trans-PdMe(OAr)(HOAr)(PMe3)2 at variable temperatures (-60 to +40 °C) indicate the presence of intramolecular alkoxide-exchange process between the alkoxide ligand and the alcohol moiety on the NMR time scale. Addition of phenol to trans-PdMe(OCH(CF3)Ph)(HOCH(CF3)Ph)(PMe3) 2 causes displacement of the alkoxide ligand by phenoxide group to give trans-PdMe(OPh)(HOCH(CF3)Ph)(PMe3)2. Reactions of trans-PdMe(OCH(CF3)Ph)(HOCH(CF3)Ph)(PMe3) 2 and trans-PdMe(OPh)(HOCH(CF3)Ph)(PMe3)2 with CO give MeCOOCH(CF3)Ph in 99% and 46% yields, respectively. Reactions of trans-PdMe(OCH(CF3)Ph)(HOCH(CF3)Ph)(PMe3) 2 with aryl esters give methylpalladium aryloxide complexes and esters of the fluorinated alcohol through exchange of the alkoxide group between the complex and the ester. The alkoxide (phenoxide) complexes catalyze transesterification of alcohols with esters. Mechanistic implications of the present results regarding the transesterification are presented.