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Highly substituted 4H-pyrans can be smoothly synthesized from readily available 2-(1-alkynyl)-2-alkene-1-ones by DBU- or n-Bu3P catalyzed hetero-[4+2] cycloaddition reactions, in which 2-(1-alkynyl)-2-alkene-1-ones act as both heterodiene and heterodinenophile.

Graphical abstract: Organocatalytic hetero [4+2] cycloaddition reactions of 2-(1-alkynyl)-2-alkene-1-ones: metal-free access to highly substituted 4H-pyrans

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