188122-53-4

Upstream product

• 188122-52-3 (E)-2-hexenyl N-[4-(trifluoromethyl)phenyl]benzimidate 
• 206360-79-4 N-(4-Trifluoromethyl-phenyl)-benzimidic acid (E)-hex-2-enyl ester 
• 206360-82-9 N-(4-Trifluoromethyl-phenyl)-benzimidic acid (Z)-hex-2-enyl ester 

Relevant academic research and scientific papers

Cyclopalladated ferrocenyl amines as enantioselective catalysts for the rearrangement of allylic imidates to allylic amides

The first examples of the use of cyclopalladated complexes in enantioselective catalysis are reported. Cyclopalladated ferrocenyl amine 6f promotes the rearrangement of some 2-alkenyl imidates to allylically transposed amides in excellent yield and moderate enantioselectivity.

Planar-chiral cyclopalladated ferrocenyl amines and imines as enantioselective catalysts for allylic imidate rearrangements

A series of enantiopure cyclopalladated ferrocenyl amines and imines were synthesized and evaluated as catalysts for the [3,3]-rearrangement of allylic benzimidates to allylic benzamides. Yields and extent of enantioselection were found to be highly depen

Palladium complexes of bis(acyclic diaminocarbene) ligands with chiral N-substituents and 8-membered chelate rings

Reaction of cis-dichloridobis(p-trifluoromethylphenylisocyanide)palladium(II) with N,N′-bis[(R)-1-phenylethyl]-1,3-diaminopropane afforded an enantiomerically pure, C1-symmetric bis(acyclic diaminocarbene)PdCl2 complex in 41% yield.

Catalytic asymmetric synthesis of chiral allylic amines. Evaluation of ferrocenyloxazoline palladacycle catalysts and imidate motifs

(Chemical Equation Presented) Palladium(II) catalysts based on a ferrocenyloxazoline palladacyclic (FOP) scaffold were synthesized and evaluated for the rearrangement of prochiral allylic N-(4-methoxyphenyl)benzimidates. When iodide-bridged dimer FOP precatalysts are activated by reaction with excess silver trifluoroacetate, the allylic rearrangement of both E and Z prochiral primary allylic N-(4-methoxyphenyl)-benzimidates takes place at room temperature to give the corresponding chiral allylic N-(4-methoxyphenyl)benzamides in high yield and good ee (typically 81-95%). Several allylic imidate motifs were evaluated also. Because the corresponding enantioenriched allylic amide products can be deprotected in good yield to give enantioenriched allylic amines, allylic N-aryltrifiuoroacetimidates were identified as promising substrates.

First Enantioselective Catalyst for the Rearrangement of Allylic Imidates to Allylic Amides

A series of Pd(II) complexes containing chiral diamine ligands were investigated as asymmetric catalysts for the rearrangement of allylic imidates to allyl amides. The best catalysts were cations obtained by dechlorination of dichloro[ (S)-2-(isoindolinylmethyl)-N-methylpyrrolidine]palladium-(II) (17) with silver salts in CH2Cl2. Catalyst 18 was studied thoroughly and shown by 1H NMR and X-ray crystallography analysis to be a C1 symmetric dimer (Figure 1). A series of related catalysts 22-27 having various counterions and anionic ligands were also prepared and studied as asymmetric catalysts for the rearrangement of allylic AT-(4-trifluorophenyl)benzimidate 29 to allylic benzamide 30 (eq 4). Rearrangement of 29 in CH2Cl2 (48 h at 40°C) in the presence of 5 mol % of 18 affords (-)-30 in 69% yield and 55% ee. Enantioselection is increased to 60% when an isomerically pure sample of 18 is employed. Chemical correlation of allylic benzamide 30 with (R)-norvaline established that (-)-30 has the R absolute configuration (Scheme 3). A cyclization-induced rearrangement mechanism (Scheme 1) requires that in the major pathway the imidate nitrogen attacks the re face of the olefin with Pd coordinated to the si face. These studies constitute the first report of asymmetric catalysis of the rearrangement of allylic imidates to allylic amides. However, significant hurdles remain to be overcome before the enantioselective rearrangement of allylic imidates becomes a practical route to enantioenriched nitrogen compounds.