<i>N</i>‐Protection Dependent Phosphorylation of Dehydroamino Acids to Build Unusual Phosphono‐Peptides

An efficient Mn(III)-promoted phosphorylation of dehydroalanine (Dha) has been developed to give unusual α-amino acids bearing phosphonates/phosphine oxides and β-vinyl phosphonates/phosphinates depending on N-protection of amino acid. N,N-diprotected dehydroalanine reacted with H-phosphonates and H-phosphine oxides to give structurally diverse phosphorylated α-amino acids through conjugate addition of phosphorous radical generated by Mn(OAc)₃.2H₂O. Whereas, a highly Z-selective phosphorylation was observed in the case of mono N-Boc protected dehydroalanine via cross dehydrogenative coupling to give (Z)- β -vinyl phosphono amino acid. The method is successfully applied to short peptides to derive unusual phosphono-peptides under mild conditions.