Selective Insertion of Alkynes into C-C σ Bonds of Indolin-2-ones: Transition-Metal-Free Ring Expansion Reactions to Seven-Membered-Ring Benzolactams or Chromone Derivatives.

An unprecedented ring expansion reaction of indolin-2-ones with alkynyl ketones under transition-metal-free conditions has been developed. Base-promoted selective cleavage of a C-C σ bond of the amide is the key in this process, which provides a straightforward and efficient way to synthesize seven-membered-ring benzolactams or chromone derivatives. The significant advantages of this method include readily accessible starting materials, wide scope and functional group tolerance, and high atom economy.