Copper(II) Triflate catalyzed amination of 1,3-dicarbonyl compounds

• Main Authors: Ton, Thi My Uyen, Himawan, Fanny, Chang, Joyce Wei Wei, Chan, Philip Wai Hong
• Other Authors: School of Physical and Mathematical Sciences
• Format: Article
• Language: English
• Published: 2013
• Online Access: https://hdl.handle.net/10356/99536; http://hdl.handle.net/10220/12901
• Institution: Nanyang Technological University

A method to prepare α,α-acyl amino acid derivatives efficiently by Cu(OTf)2+1,10-phenanthroline (1,10-phen)-catalyzed amination of 1,3-dicarbonyl compounds with PhI[DOUBLE BOND]NSO2Ar is described. The mechanism is thought to initially involve aziridination of the enolic form of the substrate, formed in situ through coordination to the Lewis acidic metal catalyst, by the putative copper–nitrene/imido species generated from the reaction of the metal catalyst with the iminoiodane source. Subsequent ring opening of the resultant aziridinol adduct under the Lewis acidic conditions then provided the α-aminated product. The utility of this method was exemplified by the enantioselective synthesis of a precursor of 3-styryl-2-benzoyl-l-alanine.