Chiral 2-aryl-2-methyl-2H-1-benzopyrans: Synthesis, characterization of enantiomers, and barriers to thermal racemization

The ease of thermal breaking of the C(sp(3))-O bond of the 2-aryl-2-methyl-2H-1-benzopyrans 1-9 was evaluated by measuring the free energy (Delta G(e)(not equal)) of the racemization reaction of optically active compounds. The variation of Delta G(e)(not equal) of the thermal ring opening in terms of structural modifications is discussed. The synthesis of the studied compounds, the preparative separation of enantiomers by liquid chromatography, the determination of enantiomeric purity, the circular dichroism of enriched enantiomers, and the measurement of rate constants of enantiomerization by monitoring the decrease of the polarimetric angle of rotation at suitable temperatures are described.