Photocatalyzed Dehydroxylative Amination of Phenols: A Ring-Expansion Approach for Medium-Sized Benzolactams.

An efficient photopromoted dehydroxylative ring-expansion approach to eight-membered benzolactams that employ phthalocyanine iron(II) as the photosensitizer has been developed. This cascade reaction protocol, featuring a visible-light-promoted dehydroxylative amination and oxidative ring-expansion lactamization of 4-hydroxyphenols with N-alkyl-4-piperidinones, provides a green and reliable approach to a diverse array of valuable eight-membered benzolactams with high chemo- and regioselectivity.