Copper(II) triflate catalyzed amination of 1,3-dicarbonyl compounds.
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=NSO(2) Ar 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.
Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371, Singapore.
Thi My Uyen
TM
Ton
Fanny
F
Himawan
Joyce Wei Wei
JW
Chang
Philip Wai Hong
PW
Chan
D000586:Amination; D000596:Amino Acids / Q000737:chemistry*; D002384:Catalysis; D003300:Copper / Q000737:chemistry*; D008698:Mesylates / Q000138:chemical synthesis / Q000737:chemistry*; D015394:Molecular Structure; D010618:Phenanthrolines / Q000737:chemistry*
D000596:Amino Acids; D008698:Mesylates; D010618:Phenanthrolines; C548824:copper(I) triflate; D003300:Copper; C025205:1,10-phenanthroline