562870-84-2

Upstream product

• 894777-24-3 2,2,2-trifluoro-N-(4-methoxyphenyl)acetimidic acid hex-2-enyl ester 
• 928-95-0 (E)-2-Hexen-1-ol 
• 928-94-9 (Z)-2-hexen-1-ol 
• 75999-66-5 (Z)-2,2,2-trifluoro-N-(4-methoxyphenyl)acetimidoyl chloride 
• 104-94-9 4-methoxy-aniline 

Relevant academic research and scientific papers

Enantioselective synthesis and application to the allylic imidate rearrangement of amine-coordinated palladacycle catalysts of cobalt sandwich complexes

The reaction of (η5-(N,N-dimethylaminomethyl)cyclopentadien- yl)(η4-tetraphenylcyclobutadiene)cobalt with sodium tetrachloropalladate and (R)-N-acetylphenylalanine gave planar chiral palladacycle di-μ-chloridebis[(η5-(Ssu

The asymmetric aza-claisen rearrangement: development of widely applicable pentaphenylferrocenyl palladacycle catalysts

Systematic studies have been performed to develop highly efficient catalysts for the asymmetric aza-Claisen rearrangement of trihaloacetimidates. Herein, we describe the stepwise development of these catalyst systems involving four different catalyst generations finally resulting in the development of a planar chiral pentaphenylferrocenyl oxazoline palladacycle. This complex is more reactive and has a broader substrate tolerance than all previously known catalyst systems for asymmetric aza-Claisen rearrange-ments. Our investigations also reveal that subtle changes can have a big impact on the activity. With the enhanced catalyst activity, the asymmetric aza-Claisen rearrangement has a very broad scope: the methodology not only allows the formation of highly enantioenriched primary allylic amines, but also secondary and tertiary amines; al-lylic amines with N-substituted quaternary stereocenters are conveniently accessible as well. The reaction conditions tolerate many important functional groups, thus providing stereoselective access to valuable functionalized building blocks, for example, for the synthesis of unnatural amino acids. Our results suggest that face-selective olefin coordination is the enantioselectivitydetermining step, which is almost exclusively controlled by the element of planar chirality.

Synthesis of nearly enantiopure allylic amines by aza-Claisen rearrangement of Z-configured allylic trifluoroacetimidates catalyzed by highly active ferrocenylbispalladacycles

The development of the first highly active enantioselective catalyst for the aza-Claisen rearrangement of Z-configured allylic trifluoroacetimidates generating valuable almost enantiopure protected allylic amines is described. Usually Z-configured allylic

Practical, highly active, and enantioselective ferrocenyl-imidazoline palladacycle catalysts (FIPs) for the aza-claisen rearrangement of N-para-methoxyphenyl trifluoroacetimidates

Just a pinch of catalyst: Just 0.05 mol % of a novel planar chiral ferrocenyl-imidazoline palladacycle catalyst (FIP) is sufficient to catalyze a highly efficient aza-Claisen rearrangement of N-para-methoxyphenyl trifluoroacetimidates and thereby provide access to chiral protected primary allylic amines with unprecedentedly high enantioselectivities (see scheme). (Chemical Equation Presented).

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.

Catalytic asymmetric rearrangement of allylic N-aryl trifluoroacetimidates. A useful method for transforming prochiral allylic alcohols to chiral allylic amines.

[reaction: see text] A useful method for the conversion of prochiral allylic alcohols to chiral allylic amines of high enantiopurity is reported. N-(4-Methoxyphenyl)trifluoroacetimidates are excellent substrates for the palladium(II)-catalyzed allylic imi