Catalytic and Enantioselective Synthesis of Inherently Chiral Saddle‐Shaped Compounds by [2 + 2 + 2] Cycloaddition of 1,8‐Naphthylene‐Based 1,10‐Diynes with Alkynoates

In this paper, we describe a chiral Rh-catalyzed [2 + 2 + 2] cycloaddition of 1,8-naphthylene-based 1,10-diynes of an anti/syn mixture with alkynoates. Thermodynamically stable saddle-shaped chiral cycloadducts were obtained in good-to-high yields and enantiomeric ratios. Hetero [2 + 2 + 2] cycloaddition using aryl cyanides also proceeded to give the corresponding inherently chiral pyridine-containing compounds.