np400313w_si_001.pdf (7.8 MB)
Cyclopeptide Alkaloids: Stereochemistry and Synthesis of the Precursors of Discarines C and D and Myrianthine A
journal contributionposted on 2016-02-19, 02:39 authored by Marco A. Mostardeiro, Vinicius Ilha, Janice Dahmer, Miguel S. B. Caro, Ionara I. Dalcol, Ubiratan F. da Silva, Ademir F. Morel
The stereochemistry of discarines C (1) and D (2) and myrianthine A (3), three cyclopeptide alkaloids isolated from Discaria febrifuga, was determined by a combination of NMR studies of 1–3, enantioselective gas chromatography, and comparison of NMR data with those of synthetic tripeptides. For the synthesis of peptides, the nonproteinogenic amino acid 3-phenylserine was also obtained in its four diastereoisomeric forms (l and d threo, obtained by recrystallization of the diastereoisomeric tripeptide, and l and d erythro, obtained by a Mitsunobu reaction with the threo-tripeptides). The general synthetic strategy described in this paper allows the tripeptide to be obtained with the free N-terminal extremity protected or dimethylated. This strategy also allows the synthesis of the corresponding peptide with an imidazolidinone ring.