Design and Synthesis of Biaryl Amino Acids and Related Catalysts with Molecular Recognition Properties

摘要

Aniline-type and DMAP-type biaryl amino acids, as well as their surrogates were developed as organocatalysts with molecular recognition properties.& para;& para;Aniline-type catalyst made regio- and stereoselective intramolecular cross-aldol reaction of unsymmetric aliphatic dial possible by fine discrimination of formyl groups. The key for discrimination of formyl groups is mild reactivity of aniline-type catalyst.& para;& para;A series of biaryl-type DMAP catalysts having an internal carboxylate ion were also developed for investigating the proper location of the carboxylate ion that effectively accelerates the DMAP catalyzed acylation (carboxylate effect). By evaluating catalytic activities of these DMAP derivatives, the carboxylate group located in close proximity to the pyridine ring in a face-to-face geometry was determined to be an effective general base to accelerate the acylation.& para;& para;Preparation of aniline-type binaphthyl amino acid via Pd catalyzed domino-coupling reaction of o-bromoaryl amides is also described in this account.