Absolute configurations of chiral herbicides determined from vibrational circular dichroism

Abstract

Enantiopure herbicides (+)-2-(4-chloro-2-methylphenoxy) propanoic acid, (+)-1 and (+)-2-(2,4-dichlorophenoxy) propanoic acid, (+)-2 were investigated using vibrational circular dichroism (VCD). Experimental absorption and VCD spectra of (+)-1 and (+)-2 in CDCl3 solution in the 2000-900 cm(-1) region were compared with the ab initio predictions of absorption and VCD spectra obtained with density functional theory using the B3LYP/6-31G* basis set for different conformers of (R)-1 and (R)-2. Due to the intermolecular hydrogen bonding, this comparison did not provide unambiguous conclusions. To eliminate intermolecular hydrogen bonding influence, the two acids 1 and 2 were converted to the corresponding methyl esters, namely, (+)-methyl 2-(4-chloro-2-methylphenoxy) propanoate, (+)-3 and (+)-methyl 2-(2,4-dichlorophenoxy) propanoate, (+)-4. The experimental VCD spectra were measured for these esters and ab initio calculations for different conformers of (R)-3 and (R)-4 were carried out. The experimental VCD spectra and corresponding population-weighted theoretical VCD spectra were found to be in excellent agreement, which allowed unambiguous determination of absolute configuration of 3 and 4 as (+)-(R). Since esterification does not invert the configuration, the absolute configuration of the parent acids 1 and 2 is the same as that of corresponding methyl esters.