Visible Light-Induced Regioselective E to Z Isomerization of Polarized 1,3-Dienes: Experimental and Theoretical Insights

The stereocontrol of E → Z isomerization on a (1E,3E)-diene, instead of a simple alkene, can be more challenging due to the increased number of isomerization possibilities. Herein, we report visible light-mediated regioselective (1E,3E → 1E,3Z) isomerization of (1E,3E)-diene. The reaction conditions are mild and easy to apply and can be applied to a wide range of substances, with an excellent yield and selectivity (90:10). It is evident from the crystal structures that the cause of regioselectivity for the isomerization of 1,3-diene may not be limited to 1,3-allylic strains; CH-π interaction may also play a vital role. Computational studies suggest that this regioselective photoisomerization is a thermodynamically feasible process and requires the accumulation of spin density on the modified double bond for the transformation to occur.