102626-53-9Relevant articles and documents
Enantioselective reduction of trifluoromethyl ketones with chiral organomagnesium amides (COMAs)
Yong, Kelvin H.,Chong, J. Michael
, p. 4139 - 4142 (2002)
(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.
Generation of Carbocations under Photoredox Catalysis: Electrophilic Aromatic Substitution with 1-Fluoroalkylbenzyl Bromides
Gu, Yucheng,Hu, Jinbo,Kuang, Cuiwen,Ni, Chuanfa,Xie, Qiqiang,Zhou, Xin
supporting information, (2020/11/13)
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.
Fine tuning of molecular and supramolecular properties of simple trianglimines-the role of the functional group
Gajewy,Szymkowiak,Kwit
, p. 53358 - 53369 (2016/06/14)
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.