Selective modification of peptides. Conversion of serine or threonine units into substituted dehydroamino acids

Trabajo presentado en "Peptides in Paris Symposium PIPS" celebrado en París del 5 al 8 de octubre de 2014.The dehydroamino acids can be found in a variety of bioactive peptides. The introduction of dehydroamino acids into synthetic analogues of bioactive peptides can increase their resistance to enzymatic degradation and allow the modulation of their biological properties. We report herein a synthetic strategy which allows the transformation of serine or threonine residues of simple peptides into dehydroamino acid units. The substrate undergoes the one-pot oxidative radical fragmentation-phosphorylation reaction, to obtain the aminophophonate, and later a Horner-Wadsworth-Emmon reaction with different aldehydes to provide peptides, with different dehydroamino acids units, in good yield and high stereoselectivity. This short, efficient procedure allows the generation of a library of peptides with dehydroamino acid units from a single starting peptideTo programs CTQ2009-07109 and SAF2013-48399-R, Ministerio de Economía y Competitividad, and European Funds FEDER/FSE. CS and DH thank their contracts to Gobierno de Canarias and CSIC, respectively.Peer Reviewe