1,4-Dibenzodiazepines, an important component of nitrogen-containing heterocycles, are widely exist in drugs. Herein, we develop a photochemical radical cascade cyclization reaction of isocyanides with α-carbonyl bromides under mild conditions. A sequence of 11-alkyl-substituted 1,4-dibenzodiazepines is produced with up to 85 yields, demonstrating excellent tolerance towards various functional groups. Primary, secondary, and tertiary α-carbonyl bromides are effectively employed as alkyl reagents.

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