SYNTHESES OF AMINO-ACID BASED PHOSPHODIESTER LINKAGE-CONTAINING CRYPTANDS AS WELL AS DIPHOSPHORYLATED MACROCYCLES

The synthesis of two amino acid based phosphodiester linkage-containin g cryptands (30 and 44) as well as diphosphorylated macrocycles (28, 2 9, 32 and 33) are described. Boc-L-Ser(Bn)-OH and/or Boc-D-Ser(Bn)-OH were used for the construction of the construction of the precursors f or the diphosphitylation and marcocyclization by phosphitylation. The carboxylic acid groups were connected with a diethylene glycol unit an d the amino functionalities were linked using (ethylenedioxy)diacetic acid, oxydiacetic acid, or an isophthalic acid derivative. The LD-cryp tands 30 and 44 were obtained after phosphitylation of the precursors 12 and 16, respectively, containing (ethylenedixoy)acetic acid or an i sophthalic acid derivative as a bottom-spacer, using 4-chlorobenzyl ph osphorodichlorodite followed by oxidation and hydrogenolysis. Phosphit ylation of the precursors containing (ethylenedioxy)acetic acid or oxy diacetic acid as bottom-spacers 11-14, using bis(4-chlorobenzyl) N,N-d iisopropylphosphoramidite and subsequent oxidation resulted in the cor responding diphosphorylated macrocycles 28, 29, 32, and 33.