Visible-Light-Promoted 6π Photocyclization of -Biaryl-Appended β-Ketoesters.

A photocatalyst- and additive-free visible-light-induced 6π-photocyclization of -biaryl-appended β-ketoesters has been developed. Upon irradiation with visible light, substrates undergo 6--trig cyclization/1,5-H shift to 9,10-dihydrophenanthren-9-ols with high efficiency and selectivity. The reaction proceeds conrotatory ring closure followed by a suprafacial 1,5-hydrogen shift leading to the observed single -fused products. Preliminary mechanistic studies reveal the feasibility of both 1,5-H shift and intersystem crossing of the diradical intermediate.