131832-00-3

Upstream product

• 576-83-0 2,4,6-trimethylphenyl bromide 
• 313-56-4 α,α,α-trifluoro-2,4,6-trimethylacetophenone 

Downstream Products

• 138689-90-4 (E)-But-2-enedioic acid bis-[(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 
• 138689-91-5 (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 
• 131832-03-6 (S)-Methoxy-phenyl-acetic acid (R)-2,2,2-trifluoro-1-(2,4,6-trimethyl-phenyl)-ethyl ester 

Relevant academic research and scientific papers

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.

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.

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.

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.