562870-93-3

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• 39520-63-3 (Z)-5-phenylpent-2-en-1-ol 
• 917-57-7 vinyllithium 
• 151918-10-4 3-phenylpropanal N-(4-methoxyphenyl)imine 
• 894777-25-4 2,2,2-trifluoro-N-(4-methoxyphenyl)acetimidic acid 5-phenyl-pent-2-enyl ester 
• 1246927-41-2 5-phenylpent-1-en-3-yl 2,2,2-trichloroacetimidate 
• 104-94-9 4-methoxy-aniline 
• 51-66-1 4-methoxyacetanilide 
• 3583-56-0 N-(4-Methoxy-phenyl)-acetimidoyl chloride 
• 376647-56-2 methyl (5-phenylpent-1-en-3-yl) carbonate 
• 75553-23-0 (E)-5-phenyl-2-penten-1-ol 
• 562870-88-6 (R)-2,2,2-trifluoro-N-(4-methoxyphenyl)-N-(1-phenylethylallyl)acetamide 

Relevant academic research and scientific papers

Cobalt-Catalyzed Regio- and Enantioselective Allylic Amination

The first earth-abundant cobalt-catalyzed highly branched- and enantioselective allylic amination of racemic branched allylic carbonates bearing alkyl groups with both aromatic and aliphatic amines has been developed. The process allows rapid access of allylic amines in high yields with exclusively branched selectivity and excellent enantioselectivities (normally 99% ee) under mild reaction conditions.

Catalytic asymmetric [3,3]-rearrangements of allylic acetimidates

A streamlined synthetic access to enantiomerically pure allylic amines as advanced and valuable synthetic building blocks is important for pharmaceutical sciences. The rearrangement of allylic trihaloacetimidates is known as an attractive method to furnis

Rhodium-catalyzed asymmetric amination of allylic trichloroacetimidates

A summary is presented of dynamic kinetic asymmetric transformations of racemic allylic trichloroacetimidates in the presence of chiral diene-ligated rhodium catalysts. The reaction is applicable to a wide variety of secondary and tertiary trichloroacetimidates containing aniline or benzylamine nucleophiles, affording nitrogen-containing tertiary and quaternary centers in good yields and with high levels of regio- and enantioselectivity. This catalytic method addresses many of the limitations previously associated with syntheses of these compounds. Georg Thieme Verlag Stuttgart - New York.

Paramagnetic palladacycles with PdIII centers are highly active catalysts for asymmetric aza-Claisen rearrangements

A combination of spectroscopic and electrochemical methods - XANES, EXAFS, X-ray, 1H NMR, EPR, Moessbauer, and cyclic voltammetry - demonstrate that the most efficient Pd catalysts for the asymmetric rearrangement of allylic trifluoroacetimidates unexpectedly possess in the activated oxidized form a PdIII center bound to a ferrocene core which remains unchanged (FeII) during the oxidative activation. These are the first recognized PdIII complexes acting as enantioselective catalysts.

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.

Studies on the bisoxazoline- and (-)-sparteine-mediated enantioselective addition of organolithium reagents to imines

The enantioselective addition of organolithium reagents to N-anisylaldimines promoted by chiral bisoxazolines and (-)-sparteine as external ligands is described. This reaction proceeds readily with a wide range of aldimine substrates (aliphatic, aromatic, olefinic) and organolithium nucleophiles (Me, n-Bu, Ph, vinyl) in excellent yields (81-99%) and with high enantioselectivities (up to 97:3.0 er). The external ligands can be used in substoichiometric amounts albeit with slightly attenuated enantioselectivities. A systematic evaluation of the structural features of the bisoxazolines revealed a primary contribution from the substituent at C(4) and a secondary influence from the bridging substituents. A computational analysis (PM3) provided a clear rationalization for the origin of enantioselectivity.

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 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