Synthesis of Novel Planar-Chiral Charge-Compensated -Carborane-Based Amino Acid.

Amino acids with unusual types of chirality and their derivatives have recently attracted attention as precursors in the synthesis of chiral catalysts and peptide analogues with unique properties. In this study, we have synthesized a new -carborane-based planar-chiral amino acid, in the molecule of which the amino group is directly bonded to the B(3) atom, and the carboxyl group is attached to the B(9) atom through the CHS(Me) fragment. 3-Amino-9-dimethylsulfonio--carborane, prepared in three steps from 3-amino--carborane in a high yield, was a key intermediate in the synthesis of the target planar-chiral amino acid. The carboxymethyl group at the sulfur atom was introduced by the demethylation reaction of the dimethylsulfonio derivative, followed by S-alkylation. The structure of new 3,9-disubstituted -carboranes was studied for the first time using NMR spectroscopy. The resonances of all boron atoms in the B NMR spectrum of 3-amino-9-dimethylsulfonio--carborane were assigned based on the 2D NMR correlation experiments. The -carborane-based planar-chiral amino acid and related compounds are of interest as a basis for peptide-like compounds and chiral ligands.