0000000000445150
AUTHOR
Nora M. Friedemann
Zwitterionic Aza-Claisen Rearrangements Controlled by Pyrrolidine Auxiliaries - Useful Key Steps in Convergent Enantioselective Syntheses
Chiral pyrrolidine substituents served as efficient auxiliaries in diastereoselective zwitterionic ketene aza-Claisen rearrangements. Palladium-catalysed N-allylation starting from optically active proline and prolinol derivatives, as well as from (2S,5S)-2,5-dimethoxymethylpyrrolidine, gave various allylamines bearing trisubstituted olefin moieties. Treatment with complex carboxylic acid fluorides in the presence of trimethylaluminium induced activated ketene addition to the nitrogen and subsequent [3,3] sigmatropic rearrangement to give γ,δ-unsaturated amides with excellent simple diastereoselectivities and up to 11:1 auxiliary-induced diastereomeric ratios. Cleavage of the pyrrolidine am…
New Optically Active 4-Alkoxyprolinol Ethers Derived from trans-4-Hydroxy-L-proline
(2S,4R)-trans-4-Hydroxy-L-proline has been used as thechiral-pool source in the efficient syntheses of optically active protected 4-hydroxyprolinols. After N-acyl protection andester formation, the first ether moiety was introduced maintaining the chiral centre adjacent to the ester. Then, reduction of the ester delivered the corresponding carbinol, which had to be alkylated selectively to avoid side reactions with the N-protecting group. Finally, the N-acyl function was removed to generate the target methyl and tert-butyl ethers displaying defined substitution patterns. The so-formed optically active 4-alkoxyprolinol ethers can be used as core fragments in biologically active compounds or …