Reductive coupling of allenyl/allyl carbonate with alkyne under dual cobalt-photoredox catalysis.

Skipped dienes are among the most prevalent motifs in a vast array of natural products, medicinal compounds, and fatty acids. Herein, we disclose a straightforward one-step reductive protocol under Co/PC for the synthesis of diverse 1,4-dienes with excellent regio- and stereoselectivity. The protocol employs allenyl or allyl carbonate as π-allyl source, allowing for the direct synthesis of skipped diene with a broad range of alkynes including terminal alkynes, propargylic alcohols, and internal alkynes. The method also demonstrated the biomimetic homologation of natural terpenols into synthetic counterparts via iterative allylation of three-carbon allyl units, employing propargylic alcohol as a readily available alkyne source. Experimental studies, control experiments, and DFT calculations suggest the dual catalytic process generates 1,3-diene from allenyl carbonate, followed by proton and electron transfer leading to Co(II)-π-allyl species prior to the alkyne coupling. The catalytic cycle transitions through Co(II), Co(I), and Co(III).