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2-Picoline efficiently catalyzes the formation of α,β-enones from acetylenedicarboxylates and aldehydes in the presence of alkenes, thereby leading to pyrans in moderate to good yields with complete regioselectivities. This synthetic method of pyrans is represented as a first example of catalytic and direct [2 + 2 + 2] cycloaddition of three different components under the metal-free conditions.

Graphical abstract: 2-Picoline catalyst-triggered [2 + 2 + 2] cycloaddition-type reaction of acetylenedicarboxylates, aldehydes and alkenes

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