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Cyclodimerization of readily accessible acetylenic ketones facilitated by a phosphane–borane complex under basic conditions is achieved. This methodology allows one-pot synthesis of phosphorus-involved tetrasubstituted furans via the construction of a C–P bond and a furan ring within a single procedure. A plausible reaction mechanism is proposed.

Graphical abstract: Towards tetrasubstituted furans through rearrangement and cyclodimerization of acetylenic ketones

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