Syntheses of amino acid based phosphodiester linkage-containing cryptands as well as diphosphorylated macrocycles

Article abstract of DOI:10.1021/jo00088a022

The syntheses of two amino acid based phosphodiester linkage-containing cryptands (30 and 44) as well as diphosphorylated macrocycles (28, 29, 32 and 33) are described. Boc-L-Ser(Bn)-OH and/or Boc-D-Ser(Bn)-OH were used for the construction of the precursors for the diphosphitylation and macrocyclization by phosphitylation. The carboxylic acid groups were connected with a diethylene glyeol unit and the amino functionalities were linked using (ethylenedioxy)diacetic acid, oxydiacetic acid, or an isophthalic acid derivative. The LD-cryptands 30 and 44 were obtained after phosphitylation of the precursors 12 and 16, respectively, containing (ethylenedioxy)acetic acid or an isophthalic acid derivative as a bottom-spacer, using 4-chlorobenzyl phosphorodichlorodite followed by oxidation and hydrogenolysis. Phosphitylation of the precursors containing (ethylenedioxy)acetic acid or oxydiacetic acid as bottom-spacers 11-14, using bis(4-chlorobenzyl) N,N-diisopropylphosphoramidite and subsequent oxidation resulted in the corresponding diphosphorylated macrocycles 28, 29, 32, and 33.