Regio-divergent nickel catalysis: intramolecular [4+2] and [2+2] cycloaddition reactions between vinylallenes and alkynes.

Vinylallenes have been recognized as versatile C2 and C4 components for nickel-catalyzed intramolecular [4+2] and [2+2] cycloadditions. The former reaction was promoted by a Ni(0) complex (up to quantitative yield), and a Ni(II) salt was a key species for the latter reaction to give the corresponding regio- and stereocontrolled cycloadducts (up to 88% yield). DFT studies revealed that both reaction pathways involve a concerted mechanism through the activation of different C-C multiple bonds in the substrates.