Regio- and stereoselective synthesis of the enantiomers of monoterpene-based β-amino acid derivatives

Abstract

The regio- and stereospecific addition of chlorosulfonyl isocyanate to cis-δ-pinene enantiomers has furnished monoterpene-fused β-lactams. The observed regioselectivity can be explained by ab initio DFT modeling of transition state structures. In contrast with the less reactive α-pinane-fused β-lactam 4, the resulting β-lactams 5 and 13 containing an amino group connected to a secondary carbon possess similar reactivity to the cycloalkane-fused analogues and can be easily converted to the β-amino acid and its protected derivatives. The base-catalyzed isomerization of the cis-amino ester afforded the corresponding trans-amino ester in moderate yield.