Transition metal-free cross-coupling of furan ring with haloacetylenes

On the example of menthofuran, a naturally abundant compound, it has been shown for the first time that the furan ring can be readily cross-coupled with acylhaloacetylenes in the solid Al(2)O(3) powder at room temperature to afford the corresponding 2-ethynyl derivatives in up to 88% yield. The reaction represents a ring closing/ring opening process that includes reversible formation of the intermediate cycloadducts further producing acetylene derivatives with elimination of HHal.