Catalytic Schmittel-Type [2+2] Cycloaddition of γ-Alkynyl Diazoacetates with Terminal Alkynes for Accessing Cyclobuta[a]indenes.

Instead of the conventional [4+2] cycloaddition, a regioselective Schmittel-type [2+2] cycloaddition of yne-allene esters, generated in situ from copper-catalyzed dediazotized coupling of γ-alkynyl diazoacetates with terminal alkynes, is reported, enabling a bicyclization process to produce a diverse array of C1-arylated cyclobuta[a]indenes in moderate to good yields. The protocol features wide functional group compatibility, mild reaction conditions, and experimental simplicity, holding significant potential for building new tricyclic cyclobutenes.