On the optical activity of the 3-aryl-4-hydroxycoumarin isolated from Millettia griffoniana: molecular modelling and total synthesis

Abstract

Semi-empirical calculations on 4-hydroxy-3-(3′,4′-methylenedioxyphenyl)-5,6,7-trimethoxycoumarin, a natural product recently isolated from Millettia griffoniana, show low rotational barriers for the C(3)–C(1′) bond (19.9 kJ mol−1) and for the inversion of the out-of-plane central 6-methoxy group (9.7 kJ mol−1). The structure of this compound is confirmed by its synthesis in 4 steps from 3,4,5-trimethoxyphenol in 37% overall yield, the key step being the ligand-coupling reaction of the 4-hydroxycoumarin 9 with 3,4-methylenedioxyphenyllead triacetate.