102626-53-9

Upstream product

• 313-56-4 α,α,α-trifluoro-2,4,6-trimethylacetophenone 
• 576-83-0 2,4,6-trimethylphenyl bromide 
• 76-05-1 trifluoroacetic acid 
• 108-67-8 1,3,5-trimethyl-benzene 
• 487-68-3 mesytaldehyde 
• 81290-20-2 (trifluoromethyl)trimethylsilane 

Downstream Products

• 131832-03-6 (S)-Methoxy-phenyl-acetic acid (R)-2,2,2-trifluoro-1-(2,4,6-trimethyl-phenyl)-ethyl ester 
• 313-56-4 α,α,α-trifluoro-2,4,6-trimethylacetophenone 
• 138689-91-5 (1S,2S,3S,4R)-Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid bis-[(R)-2,2,2-trifluoro-1-(2,4,6-trimethyl-phenyl)-ethyl] ester 
• 138689-91-5 (1S,2R,3R,4R)-Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid bis-[(R)-2,2,2-trifluoro-1-(2,4,6-trimethyl-phenyl)-ethyl] ester 
• 138689-89-1 (1S,2S,4S)-Bicyclo[2.2.1]hept-5-ene-2-carboxylic acid (S)-2,2,2-trifluoro-1-(2,4,6-trimethyl-phenyl)-ethyl ester 
• 138689-89-1 (1S,2S,4S)-Bicyclo[2.2.1]hept-5-ene-2-carboxylic acid (R)-2,2,2-trifluoro-1-(2,4,6-trimethyl-phenyl)-ethyl ester 
• 138689-88-0 Acrylic acid (R)-2,2,2-trifluoro-1-(2,4,6-trimethyl-phenyl)-ethyl ester 
• 139050-56-9 (R)-3,3,3-Trifluoro-2-methoxy-2-phenyl-propionic acid (R)-2,2,2-trifluoro-1-(2,4,6-trimethyl-phenyl)-ethyl ester 
• 138689-90-4 (E)-But-2-enedioic acid bis-[(R)-2,2,2-trifluoro-1-(2,4,6-trimethyl-phenyl)-ethyl] ester 

Relevant academic research and scientific papers

Enantioselective reduction of trifluoromethyl ketones with chiral organomagnesium amides (COMAs)

(formula presented) Chiral organomagnesium amides (COMAs), readily prepared from dialkylmagnesiums and chiral secondary amines, can reduce trifluoromethyl ketones to form secondary alcohols with excellent enantioselectivities (up to 98:2 er) and chemical yields (typically ≥95% conversion, ≥85% isolated yields). These MPV-type reductions use an achiral hydride source, and the chiral amine is readily recovered.

Photoredox-Catalyzed Ring-Opening Addition Reaction between Benzyl Bromides and Cyclic Ethers

A novel nucleophilic reaction between cyclic ethers and benzyl bromides is achieved under photoredox catalysis. The reaction proceeds through a single-electron-transfer (SET) pathway rather than a common SN2 mechanism. By two steps of reduction and oxidation, a benzyl bromide heterolyzes to give a carbocation and bromide ion under mild conditions, and then a cyclic ether captures both the carbocation and bromide ion to afford the addition product.

Generation of Carbocations under Photoredox Catalysis: Electrophilic Aromatic Substitution with 1-Fluoroalkylbenzyl Bromides

A novel Friedel-Crafts-type alkylation of arenes to access valuable 1-fluoroalkyl-1,1-biaryl compounds is established under mild conditions. The key to success is the efficient generation of a destabilized benzylic carbocation intermediate via two consecutive single-electron transfer processes by virtue of visible-light photoredox catalysis. This unique activation pattern avoids using strong Lewis acids and high temperatures that are required for generation of destabilized carbocations in traditional Friedel-Crafts reactions. This protocol demonstrates the first example of photoredox-catalyzed heterolysis of electronically deactivated benzylic C-Br bonds for the formation of destabilized carbocation intermediates.

Palladium-Catalyzed Suzuki–Miyaura Cross-Coupling of Secondary α-(Trifluoromethyl)benzyl Tosylates

A palladium-catalyzed C(sp3)?C(sp2) Suzuki–Miyaura cross-coupling of aryl boronic acids and α-(trifluoromethyl)benzyl tosylates is reported. A readily available, air-stable palladium catalyst was employed to access a wide range of functionalized 1,1-diaryl-2,2,2-trifluoroethanes. Enantioenriched α-(trifluoromethyl)benzyl tosylates were found to undergo cross-coupling to give the corresponding enantioenriched cross-coupled products with an overall inversion in configuration. The crucial role of the CF3 group in promoting this transformation is demonstrated by comparison with non-fluorinated derivatives.

Fine tuning of molecular and supramolecular properties of simple trianglimines-the role of the functional group

Chiral, triangular poly-azamacrocycles (trianglimines) readily available from enantiomerically pure trans-1,2-diaminocyclohexane and various aromatic dialdehydes, differ in their nature and substitution pattern. The highly symmetrical macrocycle having two electron-donating groups attached to the aryl moieties is formed under thermodynamic control that fulfilled the so called entropy of symmetry rule. Conversely, from the 2-nitroterephthaldehyde a kinetic product of trivial C1 symmetry is solely obtained, whereas from 2-methoxyterepthaldehyde a mixture of C3- and C1-symmetrical macrocycles are formed. The factors that contribute to the mechanism of the macrocycle formation were determined on the basis of an experimental/theoretical approach. The non-symmetrical structure of the macrocycle resulted from a symmetrical intermediate that appeared during cyclocondensation. The chiroptical properties of the trianglimines were studied by means of experimental ECD and VCD methods supported by quantum-chemical calculations. The nitro-substituted trianglimine appeared to be a simple, low molecular weight supergelator forming in polar media of stable chiral organogels. The structure of the gel is affected by the nature and chirality of the dopant. The hexaimine macrocycles after reduction of the CN imine bonds formed trianglamines-useful chiral ligands in stereoselective synthesis. The Zn-trianglamine complexes were employed as catalysts for asymmetric hydrosilylation of prochiral ketones, providing products of enantiomeric excess up to 98%. This remains the best result obtained for Zn-diamine catalysed asymmetric hydrosilylation of ketones so far.

Development of (Trifluoromethyl)zinc Reagent as Trifluoromethyl Anion and Difluorocarbene Sources

The trifluoromethylation of carbonyl compounds is accomplished by the stable (trifluoromethyl)zinc reagent generated and then isolated from CF3I and ZnEt2, which can be utilized as a trifluoromethyl anion source (CF3-). The reaction proceeds smoothly with diamine as a ligand and ammonium salt as an initiator, providing the corresponding trifluoromethylated alcohol products. Moreover, the (trifluoromethyl)zinc reagent can also be employed as a difluorocarbene source (:CF2) not only for gem-difluoroolefination of carbonyl compounds with phosphine but also for gem-difluorocyclization of alkenes or alkynes via the thermal decomposition, respectively.

Asymmetric hydrosilylation of ketones catalyzed by complexes formed from trans-diaminocyclohexane-based diamines and diethylzinc

Chiral acyclic and macrocyclic amines derived from trans-1,2- diaminocyclohexane in complexes with diethylzinc efficiently catalyze asymmetric hydrosilylation of aryl-alkyl and aryl-aryl ketones with enantiomeric excess of the product up to 86 %. A trianglamine ligand with a cyclic structure or the presence of an additional coordinating group increases the enantioselectivity of the reaction, in comparison with catalysis by a simple acyclic N,N′-dibenzyl-1,2-diaminocyclohexane ligand. In addition, the effect of the asymmetric activation of the catalyst by a variety of alcohols and diols is studied.

Convenient enantioselective hydrosilylation of ketones catalyzed by zinc-macrocyclic oligoamine complexes

Chiral macrocyclic tetra- and hexamine macrocycles derived from trans-1,2-diaminocyclohex-ane (DACH) in complexes with diethylzinc efficiently catalyze the asymmetric hydrosilylation of aryl alkyl ketones with enantiomeric excess of the product up to 89%. The cyclic structure of the triangla-mine ligand increases the enantioselectivity of the reaction, in comparison to the catalysis with the acyclic N,N′-dibenzyl-DACH ligand. Density functional theory (DFT) computations on the structures of ligand-zinc complexes and on the structures of these complexes with a coordinated acetophenone mole-cule allow us to rationalize the direction of the asymmetric induction of the hydrosilylation reaction as well as the superiority of the cyclic ligand compared to the acyclic one. This is the first example of asymmetric catalysis for the hydrosilylation reaction of ketones with the use of a readily available, inexpensive, and reusable macrocyclic trianglamine ligand.

Remarkably effective and simple syntheses of enantiomerically pure secondary carbinols from achiral ketones

The chiral oxazaborolidine (1)-catalyzed reduction of the ketones 2, 6 and 8 has provided simple access to the chiral secondary carbinols 3, 7, and 9 in very high enantiomeric purity.